Structural and thermal studies of PVA:NH4I

Proton-conducting polymer electrolytes based on poly vinyl alcohol (PVA; 88% hydrolyzed) and ammonium iodide (NH₄I) has been prepared by solution casting method with different molar ratios of polymer and salt using DMSO as solvent. DMSO has been chosen as a solvent due its high dielectric constant and also its plasticizing nature. The ionic conductivity has been found to increase with increasing salt concentration up to 25 mol% beyond which the conductivity decreases and the highest ambient temperature conductivity has been found to be 2.5×10⁻³ S cm⁻¹. The conductivity enhancement with addition of NH₄I has been well correlated with the increase in amorphous nature of the films confirmed from XRD and differential scanning calorimetry (DSC) analyses. The temperature-dependent conductivity follows the Arrhenius relation. The polymer-proton interactions have been analyzed by FTIR spectroscopy.     

AC impedance studies on proton-conducting PAN : NH4SCN polymer electrolytes

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

An investigation of PVdF/PVC-based blend electrolytes with EC/PC as plasticizers in lithium battery applications

Solid polymer electrolytes (SPEs) composed of poly(vinylidene fluoride) (PVdF)-poly(vinyl chloride) (PVC) complexed with lithium perchlorate (LiClO₄) as salt and ethylene carbonate (EC)/propylene carbonate (PC) as plasticizers were prepared using solvent-casting technique, with different weight ratios of EC and PC. The amorphicity and complexation behavior of the polymer electrolytes were confirmed using X-ray diffraction (XRD) and FTIR studies. TG/DTA and scanning electron microscope (SEM) studies explained the thermal stability and surface morphology of electrolytes, respectively. The prepared thin films were subjected to AC impedance measurements as a function of temperature ranging from 302 to 373 K. The temperature-dependence conductivity of polymer films seems to obey VTF relation.     

Effect of dibutyl phthalate as plasticizer on high-molecular weight poly(vinyl chloride)–lithium tetraborate-based solid polymer electrolytes

A series of different composition of polymer electrolytes-based on poly(vinyl chloride) (PVC) as host polymer, lithium tetraborate (Li₂B₄O₇) as dopant salt, and dibutyl phthalate (DBP) as plasticizer were prepared by solution casting method. The interaction between the PVC, Li₂B₄O₇, and DBP were studied by Fourier transform infrared. The shifting, broadening, and splitting of transmission peaks were the evidences of complexation. The highest ionic conductivity polymer electrolyte of 2.83 × 10⁻⁶ S/cm was achieved at ambient temperature upon addition of 30 wt.% of DBP. In addition, the temperature-dependent conductivity, frequency-dependent conductivity, dielectric permittivity, and modulus studies were performed. The temperature-dependent conductivity of the polymer electrolytes was found to obey the Arrhenius behavior. The thermal stability of polymer electrolytes was verified by thermogravimetric analysis. The lower in glass transition temperature was proven in differential scanning calorimetry, whereas the higher amorphous region within the polymer matrix was demonstrated in X-ray diffraction.     

Structure, thermal and transport properties of PVAc-LiClO4 solid polymer electrolytes

The lithium ion conducting solid polymer electrolytes (SPE) based on PVAc-LiClO₄ of various compositions were prepared by solution casting technique. Structure and surface morphology characterization were studied by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) measurements, respectively. Thermal and conductivity behavior of polymer-salt complexes were studied by employing differential scanning calorimetry (DSC) and ac impedance measurements, respectively. XRD and SEM analyses indicate the amorphous nature of the polymer-salt complexes. DSC measurements show decrease in T_g with the increase in LiClO₄ concentrations. The bulk conductivity of the PVAc:LiClO₄ polymer electrolytes was found to vary between 7.6×10⁻⁷ and 6.2×10⁻⁵ S cm⁻¹ at 303 K with the increase in salt concentration. The temperature dependence of the polymer electrolyte complexes appear to obey Arrhenius law.     

Electrical,structural, and morphological studies of honeycomb-like microporous zinc-ion conducting poly (vinyl chloride)/poly (ethyl methacrylate) blend-based polymer electrolytes

Solid polymer electrolytes (SPEs) based on poly (vinyl chloride)/poly (ethyl methacrylate) [PVC/PEMA] blend complexed with zinc triflate [Zn(CF₃SO₃)₂] salt have been prepared using solution casting technique. Thin film samples containing various blend ratios of PVC/PEMA with fixed composition of salt have been examined by means of complex impedance analysis, and as a consequence, the typical composition corresponding to PVC (30 wt%)/PEMA (70 wt%) has been identified as the optimized blend exhibiting the highest room temperature ionic conductivity of 10^?8 Scm^?1. The ionic conductivity of the optimized blend was further enhanced from 10^?8 to 10^?6 Scm^?1 by adding the chosen salt in different weight percentages at 301 K. The occurrence of complexation of the polymer blend and an evidence of interaction of cations, namely Zn²⁺ ions with the polymer blend, have been confirmed by Attenuated total reflectance-Fourier transformed infrared (ATR-FTIR) spectroscopy measurement studies. The efficacy of ion-polymer interactions was estimated by means of an evaluation of transport number data pertaining to Zn²⁺ ions which was found to be 0.56. The apparent changes resulting in the structural properties of these polymer electrolytes possessing a honeycomb-like microporous structure were identified using X-ray diffraction (XRD) and scanning electron microscopic (SEM) studies. Such promising features of the present polymer blend electrolyte system appear to suggest possible fabrication of new rechargeable zinc batteries involving improved device characteristics.     

Effects of Al2O3 nanofiller and EC plasticizer on the ionic conductivity enhancement of solid PEO-LiCF3SO3 solid polymer electrolyte

A solid polymer electrolyte (SPE) is synthesized by solution casting technique. The SPE uses poly(ethylene oxide) PEO as a host matrix doped with lithium triflate (LiCF₃SO₃), ethylene carbonate (EC) as plasticizer and nano alumina (Al₂O₃) as filler. The polymer electrolytes are characterized by Impedance Spectroscopy (IS) to determine the composition of the additive which gives the highest conductivity for each system. At room temperature, the highest conductivity is obtained for the composition PEO-LiCF₃SO₃-EC-15%Al₂O₃ with a value of 5.07 10^− 4 S/cm. The ionic conductivity of the polymer electrolytes increases with temperature and obeys the Arrhenius law. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) studies indicate that the conductivity increase is due to an increase in amorphous content which enhances the segmental flexibility of polymeric chains and the disordered structure of the electrolyte. Fourier transform infrared spectroscopy (FTIR) spectra show the occurrence of complexation and interaction among the components. Scanning electron microscopy (SEM) images show the changes morphology of solid polymer electrolyte.     

Novel electrospun PAN�CPVC composite fibrous membranes as polymer electrolytes for polymer lithium-ion batteries

Composite fibrous membranes based on poly(acrylonitrile)(PAN)-poly(vinyl chloride)(PVC) have been prepared by electrospinning. The fibrous membranes are made up of fibers of 850- to 1,300-nm diameters. These fibers are stacked in layers to produce a fully interconnected pore structure. Polymer electrolytes were prepared by immersing the fibrous membranes in 1 M LiClO₄-PC solution for 60 min. The condition of pure PAN polymer electrolytes is jelly, which has poor mechanical performance and cannot be used. But when PVC with a good mechanical stiffener was added to PAN, the condition of composite PAN?CPVC polymer electrolytes becomes free-standing. In addition, the optimum electrochemical properties have been observed for the polymer electrolyte based on PAN?CPVC (8:2, w/w) to show ionic conductivity of 1.05?×?10^?3 S cm^?1 at 25 °C, anodic stability up to 4.9 V versus Li/Li⁺, and a good compatibility with lithium metal resulting in low interfacial resistance. The promising results showed that fibrous PEs based on PAN?CPVC (8:2, w/w) have good mechanical stability and electrochemical properties. This shows a great potential application in polymer lithium-ion batteries.     

Effect of lithium salt concentration in PVAc/PMMA-based gel polymer electrolytes

Hybrid solid polymer electrolyte films comprising of poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), LiClO₄, and propylene carbonate are prepared by solution casting technique by varying the salt concentration. In this study, PVAc/PMMA polymer blend ratio is fixed as 25:75 on the basis of conductivity and mechanical stability of the film. X-ray diffraction, Fourier transform infrared impedance, thermogravimetry/differential thermal analysis and scanning electron microscopy studies are carried out for the polymer electrolytes. The maximum ionic conductivity is found to be 4.511 × 10⁻⁴ S cm⁻¹ at 303 K for the plasticized polymer electrolyte with 8 wt.% of LiClO₄. The ionic conductivity is found to decrease with an increase of LiClO₄ concentration.     

Synthesis and characterization of proton-conducting polymer electrolyte based on polyacrylonitrile (PAN)

Solid polymer electrolytes based on polyacrylonitrile (PAN) doped with ammonium iodide (NH₄I) have been prepared by solution casting method with different molar ratios of polymer and salt using DMF as solvent. The XRD pattern confirms the dissociation of salt. The FTIR analysis confirms the complex formation between the polymer and the salt. A shift in glass transition temperature (T _g ) of the PAN/NH₄I electrolytes has been observed from the DSC thermograms, which indicates the interaction between the polymer and the salt. The conductivity analysis shows that the polymer electrolyte with 20 mol% NH₄I has the highest conductivity equal to 1.106 × 10⁻³ S cm⁻¹ at room temperature. The activation energy (E _a ) has been found to be low for the highest conductivity sample. The dielectric permittivity (ε*) and modulus (M*) have been calculated from the alternating current (AC) impedance spectroscopy in the frequency range 42 Hz–1 MHz. The DC polarization measurement shows that the conductivity is mainly due to ions.

     

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.     

Thermal and electrochemical properties of poly(butylene sulfite)-based polymer electrolyte

Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO₂CF₃)₂, LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO₂F)₂, LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36?×?10^?4 S/cm at 80 °C and 1.01?×?10^?5 S/cm at 20 °C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25?×?10^?3 S/cm at 80 °C and 5.93?×?10^?5 S/cm at 20 °C. Glass transition temperature (T _g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T _g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.     

Structural,electrical conductivity,and transport analysis of PAN–NH<Subscript>4</Subscript>Cl polymer electrolyte system

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

Proton-conducting polymer electrolyte based on PVA-PAN blend doped with ammonium thiocyanate

Blending of polymers is one of the most useful methods for modulating the conductivity of solid polymer electrolytes. Blend polymer electrolytes have been prepared with polyvinyl alcohol (PVA)-polyacrylonitrile (PAN) blend doped with ammonium thiocyanate with different concentrations by solution casting technique, using dimethyl formamide (DMF) as the solvent. The prepared electrolytes are characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR), ultraviolet (UV), and ac impedance measurement techniques. The increase in amorphous nature of the blend polymer electrolyte by the addition of salt is confirmed by XRD analysis. The complex formation between the polymers and the salt has been confirmed by FTIR analysis. The thermal behavior has been examined using DSC and TGA. The maximum conductivity has been found to be 2.4?×?10^?3 S cm^?1 for 92.5PVA/7.5PAN/25 % NH₄SCN sample at room temperature. The temperature dependence of conductivity has been studied with the help of Arrhenius plot, and the activation energies are calculated. The proton conductivity is confirmed by dc polarization measurement technique. ¹H NMR studies reveal the presence of protons in the sample. A proton battery is constructed with the highest conducting sample, and its open circuit voltage is measured to be 1.2 V     

Structural, thermal, and conductivity studies of high molecular weight poly(vinylchloride)-lithium triflate polymer electrolyte plasticized by dibutyl phthalate

Poly(vinylchloride) (PVC) is an insulator and acts as a host in polymer electrolyte systems where addition of inorganic salt lithium trifluoromethanesulfonate (LiCF₃SO₃) and dibutyl phthalate (DBP) converts the system to become conductor. The conductivity of polymer electrolytes is explained on the basis of ionic mobility. Thirty-five weight percent DBP plasticized polymer electrolyte has the highest conductivity value (3.30?×?10^?9 S cm^?1) at 303 K. Temperature dependence of the conductivity of polymer films obeys the Arrhenius rule. X-ray diffraction (XRD) proves that addition of DBP will increase the amorphous nature of the system and lead to enhancement in ionic conductivity. Complexation between high molecular weight PVC, LiCF₃SO₃, and DBP is confirmed by the shifting of peaks, decreasing of peaks intensity, and broadening of peaks in XRD. Thermogravimetric analysis reveals that addition of DBP to PVC–LiCF₃SO₃ system reduces the stability of the film. Subsequently, thermal stability decreases with the increase in DBP content in the polymer electrolytes.     

Ionic conduction in plasticized PVC/PAN blend polymer electrolytes

Blended polymer electrolytes with poly(vinyl chloride) (PVC)–poly(acrylonitrile) (PAN) were prepared with different plasticizer concentrations and constant lithium perchlorate (LiClO₄) ratio by the solution-casting technique. The structure and complexation of the prepared films were studied by X-ray diffraction and Fourier transform infrared spectroscopy. The effect of the plasticizer on the ionic conduction in these electrolytes was investigated using alternating current impedance measurement and discussed. The temperature-dependant ionic conductivity was carried out in the range 302–373 K. The prepared films were also examined by thermogravimetry/differential thermal analysis to determine their thermal stability.     

Conductivity and thermal studies of blend polymer electrolytes based on PVAc–PMMA

The polymer electrolytes comprising blend of poly(vinyl acetate) (PVAc) and poly(methylmethacrylate) (PMMA) as a host polymer and LiClO₄ as a dopant are prepared by solution casting technique. The amorphous nature of the polymer–salt complex has been confirmed by XRD analysis. The DSC thermograms show two T_g's for PVAc–PMMA blend. A decrease in T_g with the LiClO₄ content reveals the increase of segmental motion. Conductance spectra results are found to obey the Jonscher's power law and the maximum dc conductivity value is found to be 1.76 × 10^− 3 S cm^− 1 at 303 K for the blend polymer complex with 20 wt.% LiClO₄, which is suitable for the Li rechargeable batteries. The conductivity–temperature plots are found to follow an Arrhenius nature. The dc conductivity is found to increase with increase of salt concentration in the blend polymer complexes.     

Synthesis and studies of new plasticized PVP: NaClO3 electrolyte system for battery applications

A new thin film sodium ion conducting plasticized polymer electrolyte based on poly(vinyl pyrrolidone) (PVP) complexed with NaClO₃ salt systems was prepared by the solution-cast method. The interaction of NaClO₃ salt with PVP was confirmed by Infrared (IR) study. Charge transport of these polymer electrolytes is due to ions, which was confirmed by Wagner’s polarization method. From the conductivity measurements, the highest conductivity value 6.71×10⁻⁵ S/cm was observed for the composition PVP:PEG:NaClO₃(30:60:10) at room temperature 35 °C. The redox behaviour and good reversibility of the plasiticized electrolytes are confirmed by electrochemical techniques. Electrochemical cell studies of these polymer electrolytes were analyzed from their discharge characteristics. The open-circuit voltage (OCV) and short-circuit current (SCC) were found to in the range of 2.52 V to 2.36 V and 760 μA to 1040 μA, respectively.     

Ionic conductivity,ionic transport and electrochemical characterizations of plastic crystal polymer electrolytes

In this work, the plastic crystal polymer electrolytes (PCPEs), composed of polyacrylonitrile (PAN), succinonitrile (SN) and lithium bis(trifluoromethane)sulfonimide (LiTFSI) were prepared. The concentrations of lithium salt were varied by weight percentage from 10 wt% to 50 wt%. The ionic conductivity of the PCPE films increases with the increase of lithium salt, where the highest value recorded is in the order of ~10^?2 S cm^?1. The temperature-dependence conductivity analysis shows that the PCPE films exhibit Arrhenius behaviour when subjected to the temperature range from 303 K to 343 K. The decrease in crystallinity was confirmed by X-ray diffraction (XRD) and Differential Scanning Calorimetry (DSC) analyses. The cationic transport number also increases with the increase of salt which corresponds well to their conductivity values. It is found that the films are electrochemically stable up to ~3.6 V as revealed by the linear sweep voltammetry (LSV) analysis. The cyclic voltammetry (CV) plots of the films shown no substantial change in the redox peaks which mean that the charge transfer reaction is reversible.     

Polymer electrolytes based on polycarbonates and their electrochemical and thermal properties

Polycarbonates (4a–d) with various side chain lengths were synthesized by the reaction of 1,4-bis(hydroxyethoxy)benzene derivatives and triphosgene in the presence of pyridine. The polymer electrolytes composed of 4a–d with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO₂CF₃)₂, LiTFSI) were prepared, and their ionic conductivities and thermal and electrochemical properties were investigated. 4d-Based polymer electrolyte showed the highest ionic conductivity values of 1.0?×?10^?4?S/cm at 80 °C and 1.5?×?10^?6?S/cm at 30 °C, respectively, at the [LiTFSI]/[repeating unit] ratio of 1/2. Ionic conductivities of these polycarbonate-based polymer electrolytes showed the tendency of increase with increasing the chain length of oxyethylene moieties as side chains, suggestive of increased steric hindrance by side chains. Unique properties were observed for the 4a(n?=?0)-based polymer electrolyte without an oxyethylene moiety. All of polycarbonate-based polymer electrolytes showed good electrochemical and thermal stabilities as polymer electrolytes for battery application.