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.

     

AC impedance studies on proton conducting polymer electrolyte complexes (PVA+CH3COONH4)

A proton conducting polymer electrolytes of pure polyvinyl alcohol and polyvinyl alcohol complexed with ammonium acetate having different compositions have been prepared by solution cast technique. FTIR spectrum confirms the complexation process. The conductivity of the pure polyvinyl alcohol is in the order 10⁻¹⁰ S/cm at ambient temperature and its value increases 10⁴ times when complexed with 20% ammonium acetate. The Arrhenius plot for all electrolyte shows two different regions above and below the glass transition temperature. A high dielectric loss value is observed for the case of complexed PVA in comparison to pure PVA. Based on the study of relaxation spectra, it is found that the relaxation time decreases with increase in temperature and dopant concentration. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Electrical conductivity studies on PVA/PVP-KOH alkaline solid polymer blend electrolyte

A series of conducting thin-film solid electrolytes based on poly (vinyl alcohol)/ poly (vinyl pyrrolidone) (PVA/PVP) polymer blend was prepared by the solution casting technique. PVA and PVP were mixed in various weight percent ratios and dissolved in 20 ml of distilled water. The samples were analyzed by using impedance spectroscopy in the frequency range between 100 Hz and 1 MHz. The PVA/PVP system with a composition of 80% PVA and 20 wt.% PVP exhibits the highest conductivity of (2.2±1.4) × 10⁻⁷ Scm⁻¹. The highest conducting PVA/PVP blend was then further studied by adding different amounts of potassium hydroxide (KOH) ionic dopant. Water has been used as solvent to prepare PVA/PVP-KOH based alkaline solid polymer blend electrolyte films. The conductivity was enhanced to (1.5 ± 1.1) × 10⁻⁴ Scm⁻¹ when 40 wt.% KOH was added. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Incorporation of NH4Br in PVA-chitosan blend-based polymer electrolyte and its effect on the conductivity and other electrical properties

Polymer electrolyte system based on poly(vinyl alcohol) (PVA)-chitosan blend doped with ammonium bromide (NH₄Br) has been prepared by solution cast method. Fourier transform infrared (FTIR) spectroscopy analysis confirms the complexation between salt and polymer host. The highest ionic conductivity obtained at room temperature is (7.68?±?1.24)?×?10^?4 S cm^?1 for the sample comprising of 30 wt% NH₄Br. X-ray diffraction (XRD) patterns reveal that PVA-chitosan with 30 wt% NH₄Br exhibits the most amorphous structure. Thermogravimetric analysis (TGA) reveals that the electrolytes are stable until ～260 °C. The conductivity variation can also be explained by field emission scanning electron microscopy (FESEM) study. Dielectric properties of the electrolytes follow non-Debye behavior. The conduction mechanism of the highest conducting electrolyte can be represented by the correlated barrier hopping (CBH) model. From linear sweep voltammetry (LSV) result, the highest conducting electrolyte is electrochemically stable at 1.57 V.     

Effect of NH4I and I2 concentration on agar gel polymer electrolyte properties for a dye-sensitized solar cell

Gel polymer electrolytes were prepared using agar polymer host, NH₄I, and I₂ salts. The sample of agar paste with 1.0 M of NH₄I and 0.2 μM of I₂ exhibits the highest conductivity and lowest viscosity values at room temperature of (2.64?±?0.19)?×?10^?3?S?cm^?1 and 1.17?±?0.29 Pa?s, respectively. All of the gel polymer electrolytes display Arrhenian behavior, and the optimum agar paste gave the lowest activation energy of 0.25 eV. It also had a good physical appearance compared with the other samples. This gel polymer electrolyte had a good potential and was applicable to a role as electrolyte in ITO-ZnO (N719 dye)/agar paste?+?1.0 M NH₄I?+?0.2 μM I₂/Au-Pd-ITO dye-sensitized solar cell.     

Structural, vibrational, thermal, and conductivity studies on proton-conducting polymer electrolyte based on poly (N-vinylpyrrolidone)

The proton-conducting polymer electrolytes based on poly (N-vinylpyrrolidone) (PVP), doped with ammonium chloride (NH₄Cl) in different molar ratios, have been prepared by solution-casting technique using distilled water as solvent. The increase in amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis confirms the complex formation of the polymer with the salt. A shift in glass transition temperature (T _g) of the PVP/NH₄Cl 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 of 15?mol% NH₄Cl-doped PVP polymer complex has been found to be maximum of the order of 2.51?×?10^?5?Scm^?1 at room temperature. The dependence of T _g and conductivity upon salt concentration has been discussed. The linear variation of the proton conductivity of the polymer electrolytes with increasing temperature suggests the Arrhenius type thermally activated process. The activation energy calculated from the Arrhenius plot for all compositions of PVP doped with NH₄Cl has been found to vary from 0.49 to 0.92?eV. The dielectric loss curves for the sample 85?mol% PVP:15?mol% NH₄Cl reveal the low-frequency ?? relaxation peak pronounced at high temperature, and it may be caused by side group dipoles. The relaxation parameters of the electrolytes have been obtained by the study of Tan?? as a function of frequency.     

Vibrational spectra of the ammonia halides NH4I and NH4F at high pressures

The vibrational spectra of ammonium iodide NH₄I at pressures up to 4.1 GPa and ammonium fluoride NH₄F at pressures up to 4.7 GPa were investigated by inelastic incoherent neutron scattering. The pressure dependences of the transverse optical translational and librational modes were obtained. The behavior of the rotational potential barrier for the ammonium ion as a function of the lattice parameter for disordered and ordered cubic phases of ammonium halides with CsCl type structure were calculated. The results obtained confirm that the transition from an orientationally disordered cubic phase into an ordered cubic phase in ammonium halides occurs at close critical values of the positional parameter of hydrogen (deuterium).     

Structural, vibrational, thermal, and electrical properties of PVA/PVP biodegradable polymer blend electrolyte with CH3COONH4

A biodegradable solid polymer blend electrolyte was prepared by using polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) polymers with different molecular weight percentages (wt.%) of ammonium acetate, and its structural, thermal, vibrational, and electrical properties were evaluated. The polymer blend electrolyte is prepared using solution casting technique, with water as a solvent. X-ray diffraction shows that the incorporation of ammonium acetate into the polymeric matrix causes decrease in the crystallinity degree of the samples. The Fourier transform infrared spectroscopy and laser Raman studies confirm the complex formation between the polymer and salt. Differential scanning calorimerty shows that the thermal stability of the polymer blend electrolyte and the glass transition temperature decreased as the concentration of ammonium acetate increased. The ionic conductivity of the prepared polymer electrolyte was found by AC impedance spectroscopic analysis. A maximum conductivity of 8.12?×?10^?5 Scm^?1 was observed for the composition of 50 PVA/50 PVP/30 wt.% of CH₃COONH₄.     

Electrical and transport properties of NH4Br-doped cornstarch-based solid biopolymer electrolyte

Ionics - In this work, cornstarch-based electrolytes are doped with ammonium bromide (NH4Br) and plasticized with glycerol. Starch-NH4Br complexation is evidenced from the Fourier transform...     

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

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

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.     

Investigation into phase diagrams of the fluorine-oxygen system: Ferroelastic-antiferroelectric (NH4)2WO2F4-(NH4)2MoO2F4

Thermal, physical, structural, optical, and dielectric investigations have been performed for oxyfluoride solid solutions (NH₄)₂W_{1 — x} Mo _x O₂F₄ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.6, 0.8, 1). The character of the influence of the chemical and hydrostatic pressures on the stability of the parent (space group Cmcm) and distorted ferroelastic and antiferroelectric phases has been determined by analyzing the temperature-pressure, unit cell volume-composition, and temperature-composition phase diagrams. The specific features of the nature and mechanism of the phase transitions have been discussed using the available data on the structural, entropy, and dielectric parameters.     

Effect of storage time on the properties of PVA–KOH alkaline solid polymer electrolyte system

Polyvinyl alcohol (PVA) and potassium hydroxide (KOH) have been used to prepare alkaline solid polymer electrolytes (ASPE) films. The films were stored in a dry environment for 30 and 100 days. The highest room temperature conductivity for the PVA:KOH film with weight percentage ratio of 1:0.67 during storage for 30 and 100 days were (8.5±0.2)×10⁻⁴ and (1.3±0.1)×10⁻⁷ S cm⁻¹, respectively. The conductivity–temperature behaviour after 30 and 100 days of storage of the alkaline polymer electrolytes is Arrhenian and liquid-like. The structural, morphological and thermal studies of the ASPE films are also presented in this paper.     

Discharge characteristics of polymer blend (PVP/PVA) electrolyte films doped with potassium bromide

Solid polymer blend electrolyte films based on PVP/PVA complexed with KBr were prepared by the solution cast technique. Various experimental techniques such as electrical conductivity and transport number measurement were used to characterize the polymer electrolyte films. Electrochemical cells with the polymer electrolytes (PVP + PVA + KBr) were fabricated in the configuration K / (PVP + PVA + KBr) / (I₂ + C + electrode). The discharge characteristics of the cells were studied under a constant load of 100 KΩ. The open-circuit voltage, short-circuit current, and discharge time for the plateau region are measured. Several other cell parameters were evaluated and are reported.     

Ion transport mechanism in proton-conducting gel-type electrolytes: solvent and polymer effects

The development and characterization of proton-conducting gel-type electrolytes containing simple aliphatic dicarboxylic acids gelled with poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP) has been investigated in the present work. The relation between the various properties and the composition of the electrolyte constituents with different electrical/physical properties has been investigated and established. Electrical properties for the developed gel-type electrolytes were found to depend upon the acidity and concentration of acid and the amount of polymer present. This dependence is explained due to the combined effect of change in ion concentration, viscosity, and physical interactions taking place between the constituents of electrolytes. Maximum conductivity of 1.59 × 10⁻³ S/cm is observed at room temperature for electrolytes containing 1 M oxalic acid. The interactions and behavior of the electrolytes are supported by Fourier transform infrared, nuclear magnetic resonance, viscosity, and pH studies.     

Effect of gamma irradiation on the polymer electrolyte PEO-NH4ClO4

Irradiation affects the structures of materials at different scales, thus changing physical and chemical properties. We study here the effect of gamma irradiation at different doses on the polymer electrolyte PEO-NH₄ClO₄. Optical micrographs show cracks in the irradiated samples and impedance spectroscopy measurements indicate reduced ion-conductivity at room temperature but slight enhancement at higher temperature. At high frequencies, the real part of the admittance shows a power-law variation; the exponent, which is a measure of self-similarity of the structure, is reduced on irradiation. The overall results point to a more disordered structure at higher radiation doses.     

TDPAC investigation on NH4Hf2F9

Time-differential perturbed angular correlation (TDPAC) measurements in NH₄Hf₂F₉ were performed between 15 and 580 K. The compound was found to be stable in the whole temperature range and no phase transitions were observed. Experimental results could be explained assuming two equally populated quadrupole interactions which suggest a neat inequivalence between the two sites occupied by the hafnium atoms in the molecule.     

Effect of PVAc dispersal into PVA-NH4SCN polymer electrolyte

The present paper deals with ion transport studies on a new proton conducting composite polymer electrolyte — (PVA_x:NH₄SCN)_y:PVAc system. Complexation and morphology of the composite electrolyte films are discussed on the basis of X-ray diffraction and differential scanning calorimetry data. Coulometry and transient ionic current measurements revealed charge transport through protons. The maximum ion conductivity was found to be 7.4·10⁻⁴ S·cm⁻¹ for the composition: x=0.15, y=0.12. The observed conductivity behaviour is correlated to the morphology of the films. The temperature dependence of the electrical conductivity exhibits Arrhenius characteristics in two different temperature ranges separated by a plateau region related to morphological changes occurring in the electrolyte.     

Spin probe ESR studies of PEGxLiClO4 polymer electrolyte systems

The technique of Electron Spin Resonance (ESR) is shown to be useful in the study of dynamics of solid polymer electrolytes (SPE). Through the ESR of the nitroxide radical (2,2,6,6-tetramethyl-1-piperidine-1-oxyl; TEMPO) dispersed in the SPE PEG₄₆LiClO₄ temperature dependence of correlation time is found. The glass transition temperature T_g is estimated to be −51 °C from the measurement of T_50G, the temperature at which the extrema separation 2A_ZZ becomes 50G and is found to be close to that measured using DSC (−51.7 °C). T_g for pure PEG-2000, which could not be measured from DSC because of its high crystallinity, is determined to be −72 °C by spin probe ESR. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Influences of LiCF3SO3 and TiO2 nanofiller on ionic conductivity and mechanical properties of PVA:PVdF blend polymer electrolyte

In recent years, solid polymer electrolytes have been extensively studied due to its flexibility, electrochemical stability, safety, and long life for its applications in various electrochemical devices. Interaction of LiCF₃SO₃ and TiO₂ nanofiller in the optimized composition of PVA:PVdF (80:20—system-A possessing σ ~ 2.8 × 10⁻⁷ Scm⁻¹ at 303 K) blend polymer electrolyte have been analyzed in the present study. LiCF₃SO₃ has been doped in system-A, and the optimized LiCF₃SO₃ doped sample (80:20:15-system-B possessing σ ~ 2.7 × 10⁻³ Scm⁻¹ at 303 K) has been identified. The effect of different concentration of TiO₂ in system-B has been analyzed and the optimized system is considered as system-C (σ ~ 3.7 × 10⁻³ Scm⁻¹ at 303 K). The cost effective, solution casting technique has been used for the preparation of the above polymer electrolytes. Vibrational, structural, mechanical, conductivity, thermal, and electrochemical properties have been studied using FTIR, XRD, stress-strain, AC impedance spectroscopic technique, DSC and TGA, LSV, and CV respectively to find out the optimized system. System-C possessing the highest ionic conductivity, higher tensile strength, low crystallinity, high thermal stability, and high electrochemical stability (greater than 5 V vs Li/Li⁺) is well suitable for lithium ion battery application.