Dielectric and conductivity relaxations in PVAc based polymer electrolytes

The polymer electrolytes composed of a blend of poly (vinyl acetate) (PVAc) and poly (methylmethacrylate) (PMMA) as a host polymer and LiClO₄ as a salt are prepared by a solution casting technique. The formation of blend polymer- salt complex has been confirmed by FT-IR spectral studies. The conductivity- temperature plots are found to follow an Arrhenius nature. Arrhenius plot shows the decrease in activation energy with the increase in salt concentration. The dielectric behaviour of the sample is analysed using dielectric permittivity (ε′), dielectric loss (ε″) and electric modulus (M″) of the samples. The impedance cole- cole plot shows the high frequency semi- circle is due to the bulk effect of the material and the depression in the semicircle shows the non-Debye nature of the material. The bulk conductivity is found to vary between 2.5×10⁻⁵ Scm⁻¹ to 1.7×10⁻³ Scm⁻¹ with the increase of salt concentration of blend polymer samples. The migration energy derived from the dissipation factor is almost equal to the activation energy calculated from conductivity. The modulus spectrum of the samples shows the non-Debye behaviour of the polymer electrolyte films. The low frequency dispersion of the dielectric constant implies the space charge effects arising from the electrodes. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Effect of counterions on the swelling of spherical polyelectrolyte brushes

We investigate the swelling of colloidal spherical polyelectrolyte brushes in the presence of different counterions. The colloidal particles consist of a solid poly(styrene) core of ca. 100 nm diameter onto which linear polyelectrolyte chains are chemically grafted. Two types of polyelectrolyte chains have been used here: The cationic polyelectrolyte poly(2-(acryloyl)ethyltrimethylammonium chloride)) (PATAC) and the anionic poly(styrenesulfonate) (PSS). Both systems are dispersed in water and the degree of swelling of the surface layer is studied by dynamic light scattering. Adding more and more salt leads to a strong shrinking of the surface layer as expected for polyelectrolyte brushes. It is shown that data obtained at low ionic strength can be collapsed on suitable master curves for monovalent and divalent counterions, respectively. For some ions, however, high salt concentrations may lead to a re-swelling of the brush layer in case of the cationic systems. This points to specific interactions of the counterions with the PATAC chains. This strong specific interaction between the counterions and the attached polyelectrolyte may even lead to flocculation of the particles at intermediate salt concentration. Surprisingly, for iodide and magnesium counterions the solubility increases again if the salt concentration is raised to 1 mol/l. Hence, specific interaction leads to salting-out effects as well as to salting-in effects for these colloidal particles. All specific effects seen at high concentrations of added salt can be explained by the increase of the reduced excluded-volume parameter which is due to the adsorption of salt ions.     

Formation of a passivating film at the lithium-PEO-LiCF3SO3 interface

The formation of a passivating film on lithium electrodes is demonstrated using ac impedance analysis. The film is formed by an electrochemical reaction between the lithium electrode and the electrolyte, which consists of poly (ethylene oxide) and LiCF₃SO₃. Effects of the salt concentration in the electrolyte and temperature on the nature and conductivity of such films are described. Data obtained from the literature for equivalent systems was interpreted according to the proposed film formation mechanism. The rate-determining step in the dissolution or deposition process of the lithium may, in some cases, be defined by the interphase film.     

Shrinking of ultrathin polyelectrolyte multilayer capsules upon annealing: A confocal laser scanning microscopy and scanning force microscopy study

Heating-induced morphological changes of micrometer size capsules prepared by step-wise deposition of oppositely charged polyelectrolytes onto melamine formaldehyde (MF) latex particles and biological cells with subsequent dissolution of the core have been investigated by confocal laser scanning microscopy (CLSM) and scanning force microscopy (SFM). For poly(styrenesulfonate-Na salt)/poly(allylamine hydrochloride) polyelectrolyte capsules a remarkable heating-induced shrinking is observed. An increase of the wall thickness corresponding to the capsule diameter decrease is found. The morphology of these microcapsules after temperature treatment is characterized. The thickening of the polyelectrolyte multilayer is interpreted in terms of a configurational entropy increase via polyanion-polycation bond rearrangement. Received 20 January 2000     

Ionic conductivity of polymer electrolytes based on phosphate and polyether copolymers

Linear polyphosphate random copolymers (LPC) composed of phosphate as a linking agent with poly(ethylene glycol) (PEG) and/or poly(tetramethylene glycol) (PTMG) were synthesized to increase local segmental motion for improved ion transport. Ionic conductivity and thermal behavior of LPC series–LiCF₃SO₃ complexes were investigated with various compositions, salt concentrations and temperatures. The PEG(70)/PTMG(30)/LiCF₃SO₃ electrolyte exhibited ionic conductivity of 8.04×10⁻⁵ S/cm at 25°C. Salt concentration with the highest ionic conductivity was considerably dependent on EO/TMO compositions in LPC series–salt systems. Relationship between solvating ability and chain flexibility with various compositions and salt concentrations was investigated through theoretical aspects of the Adam–Gibbs configurational entropy model. Temperature dependence on the ionic conductivity in LPC6 series–salt systems suggested the ion conduction follows the Williams–Landel–Ferry (WLF) mechanism, which is confirmed by Vogel–Tamman–Fulcher (VTF) plots. The ionic conductivity was affected by segmental motion of the polymer matrix. VTF parameters and apparent activation energy were evaluated by a non-linear least square minimization method. These results suggested that the solvating ability of the host polymer might be a dominant factor to improve the ionic conductivity rather than chain mobility.     

High-pressure conductivity studies of blends of poly(p-phenylene)s with oxyethylene side-chains and lithium salts

High-pressure electrical conductivity studies have been carried out with poly(p-phenylene)s with oxyethylene side-chains (PPP(EO)_x/y), which were blended with LiCF₃SO₃. Measurements were performed at pressures up to 280 MPa and at different temperatures. The influences of salt concentration, side-chain length, temperature, and plasticizer content on the relative conductance and activation volume are investigated. The temperature-dependent conductivity of the sample is non-Arrhenius and exhibits Williams–Landel–Ferry (WLF) behavior. The logarithm of relative conductance for PPP(EO)_x/y/LiCF₃SO₃ decreases almost linearly with increasing pressure but increases with salt concentration and side-chain length. As temperature increases, the activation volume becomes smaller but remains positive for PPP(EO)_x/y/LiCF₃SO₃. At higher salt concentrations and longer side-chain lengths, a smaller activation volume for the ion motion is found. These results can be interpreted such that PPP(EO)_x/y/LiCF₃SO₃ behaves like a true polymer electrolyte where ion transport is mediated by segmental motions of the EO side-chains. The addition of tetraethylene glycol dimethyl ether (TEGDME) as a plasticizer increases the activation volume but reduces the conductance.     

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.     

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.     

Conductivity and dielectric relaxation of Li salt in poly(ethylene oxide) and epoxidized natural rubber polymer electrolytes

Two types of polymer electrolytes were studied: poly(ethylene oxide) (PEO) and epoxidized natural rubber (ENR) both filled with lithium perchlorate. Universal dielectric behavior and impedance relaxation were investigated at room temperature over a wide range of salt concentration. Complex impedance plots exhibit one semicircle in some cases (PEO polymer electrolytes) with an extended spike at low frequencies. This implies a double layer capacity strongly influences conductivity at low frequencies. In the ENR–salt system, semicircles can be obtained only at very high concentrations. This points towards stable resistor dominated networks only develop at very high salt concentrations for this system. Centers of the semicircles lie below real axis indicating non-Debye dielectric relaxation. The relaxation peak broadens and shifts to higher frequencies with increasing salt content. It indicates that the relaxation time of polarization relaxations decreases with ascending salt content. Relaxations occur at extremely low salt concentrations in PEO and only at very high salt concentrations in ENR. Hence, conductivity of ENR–salt is one to two orders of magnitude lower as for PEO–salt.     

Evaporation of saline colloidal droplet and deposition pattern

The dynamic process of the evaporation and the desiccation of sessile saline colloidal droplets, and their final deposition are investigated. During the evaporation, the movement of the colloidal particles shows a strong dependence on the salt concentration and the droplet shape. The final deposition pattern indicates a weakened coffee-ring effect in this mixed droplet system. The microscopic observation reveals that as evaporation proceeds, the particle motion trail is affected by the salt concentration of the droplet boundary. The Marangoni flow, which is induced by surface tension gradient originating from the local evaporative peripheral salt enrichment, suppresses the compensation flow towards the contact line of the droplet. The inhomogeneous density and concentration field induced by evaporation or crystallization can be the major reason for various micro-flows. At last stage, the distribution and crystallization of Na Cl are affected by the colloidal particles during the drying of the residual liquid film.     

Charge carriers dynamics in PEO + NaSCN polymer electrolytes

Sodium-ion-conducting poly(ethylene oxide) (PEO)-based solid polymer electrolyte films mixed with salt sodium thiocyanate (NaSCN) have been prepared by solution-cast method. Films were characterized in detail using optical microscopy, differential scanning calorimetry, and impedance spectroscopy. The drop in ionic conductivity with increasing salt concentration is supported by a decrease in number of charge carriers. Dielectric constant is supported by decreases in numbers of charge carriers and increase in mobility. The maximum ionic conductivity and number of charge carriers for material are found 9.86 × 10^?6 S/m and 1.21 × 10²⁰, respectively, for weight % ratio (95:05) of PEO:NaSCN polymer salt complex. The maximum mobility of material is found 2.58 × 10^?6 m²/Vs for weight % ratio (80:20) of PEO:NaSCN polymer salt complex.     

A Molecular Dynamics study of the influence of side-chain length and spacing on lithium mobility in non-crystalline LiPF6·PEOx; x = 10 and 30

Molecular Dynamics (MD) simulation techniques have been used to investigate systematically how the length and spacing of poly(ethylene oxide) (PEO) side-chains along a PEO backbone influence ion mobility for two different salt concentrations. This is of fundamental relevance to the design of new polymer electrolytes for battery applications. The salt used has been LiPF₆ in concentrations corresponding to Li:EO ratios of 1:30 and 1:10. The MD box contained PEO backbones of 89–343 EO units to which 3, 6, 7, 8, 9 and 15 EO unit side-chains were added. The selected spacings along the backbone between the PEO side-chains attachment points were 5, 10, 15, 20 and 50 EO units. The backbone and all side-chains were methoxy end-capped, and the simulations were all made at 293 K. Ion mobilities have been estimated from the variation of mean-square-displacement with time, and have been analysed in relation to chain dynamics, cross-linking and ion pairing. Comparisons are also made with the results of simulated PEO systems without side-chains and/or without salt. It is found that, at a higher concentration, many short side-chains give the highest ion mobility, while the mobility is highest for side-chain lengths of 7–9 EO units at the lower concentration.     

Ionic conductivity, thermal stability and FT-IR studies on plasticized PVC / PMMA blend polymer electrolytes complexed with LiAsF6 and LiPF6

The lithium salt (x) (x=LiAsF₆, LiPF₆) was complexed with a blend of poly(vinyl chloride) (PVC) / poly(methyl methacrylate)(PMMA) and plasticized with a combination of ethylene carbonate(EC) and propylene carbonate(PC). The electrolyte films were prepared using doctor blade method and subjected to ionic conductivity measurements at nine different temperatures viz.,-30, -15, 0, 15, 30, 40, 50, 60 and 70 °C. The films were also subjected to TG - DTA and FT-IR analysis. The effect of salt on ionic conductivity is discussed. A 75:25 PMMA/PVC blend at 60 % plasticizer content has been found to possess optimal properties in terms of ionic conductivity, thermal and electrochemical stability.     

Role of salt concentration on conductivity optimization and structural phase separation in a solid polymer electrolyte based on PMMA-LiClO4

Although a large number of ionic conductors based on poly(methyl-methacrylate) (PMMA) are reported in literature, an optimization of salt concentration with respect to conductivity and stability properties remains by and large neglected. We report, perhaps for the first time, such an optimization of salt (LiClO₄) concentration on structural, morphological, electrical, and ion–polymer interaction in PMMA-based solid polymer films. The active coordination site for the cation (Li⁺), out of the two possible electron donating functional groups (i.e. C=Ö and Ö–CH₃) in PMMA, has been ascertained on the basis of evidences recorded in Fourier transform infrared spectrum. The results suggested C=Ö as the only possible site in PMMA matrix for coordination with Li⁺ cation. The X-ray diffraction results have clearly indicated an optimum limit of salt dissolution in PMMA matrix corresponding to O/Li = 4 (i.e., ~21wt.%) above which “phase-separation” occurs distinctly. The effect of salt concentration on amorphous → crystalline phase changes in PMMA and its correlation to morphology have been clearly observed in terms of their impact on electrical properties. An optimum electrical conductivity of ~7.2 × 10^?5S cm^?1 has been recorded at 100°C (~PMMA glass transition). The temperature dependence of conductivity follows typical Vogel–Tamman–Fulcher behavior.     

Rheological properties and impedance spectroscopy of PMMA-PVdF blend and PMMA gel polymer electrolytes for advanced lithium batteries

In the present study, blend ionic conducting membranes formed by poly(methylmethacrylate (PMMA) / poly(vinilydenefluoride) (PVDF) (blend ratio PMMA/PVdF=80/20), lithium perchlorate (LiClO₄) as a salt and a mixture of ethylene carbonate (EC)-propylene carbonate (PC) as plasticizer are prepared and characterized by impedance spectroscopy and dynamic rheological experiments. We compared the results obtained on the blends with those on PMMA gel-based polymer electrolytes incorporating the same EC/PC mixture of plasticizer and the same quantities of salt. The main focus of this study is to illustrate the rheological data of the gels and blends electrolytes to point up their mechanical stability with the temperature in sight of the technological application. The conductivity values are reported in the 20–100 °C temperature range for different lithium salt contents, while the rheological behaviour has been recorded up to 140 °C. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Raising the softening temperature of poly(vinylidene fluoride) gel electrolytes

Factors affecting the softening temperature of polymer gel electrolytes (PGEs) made from poly(vinylidene fluoride) (PVDF) have been investigated. The melting temperature transition has been found to rise with increased polymer concentration and salt concentration but reduced by solvent dielectric constant. The solvent dielectric constant was reduced by mixing propylene carbonate (PC) with the non-solvent phenyl propanol (PhP). The use of lithium salt bis(oxalate)borate (LiBOB) in place of lithium tetrafluroborote (LiBF₄) gives further enhancement to the softening temperature of PGEs. In all of those cases, there is an eventual trade-off between increased softening temperature and reduced ionic conductivity, in this fabricated gel electrolyte. Here, a variety of ways to tailor the properties of PGEs for different applications has been shown.     

Preparation and Swelling Behavior of Partially Hydrolyzed Polyacrylamide Nanocomposite Hydrogels in Electrolyte Solutions

In this research, nanocomposite hydrogels were prepared by cross‐linking of partially hydrolyzed polyacrylamide/sodium montmorillonite aqueous solutions with chromium triacetate. The gelation process and influence of nanoclay content and salt concentration on swelling behavior were investigated. Study of gelation behavior using dynamic rheometry method showed that increasing the nanoclay content decreases the storage modulus, due to the partial adsorption of polymer chains onto the clay surface and ionic interaction between negative layers of sodium montmorillonite and Cr.³⁺ By increasing the cross‐linker concentration of the gelation system, the viscous energy dissipation properties of the nanocomposite gel decreases. Swelling ratio of the nanocomposite gels in distilled water decreased as the concentration of the nanoclay increased. However, nanocomposite gels showed lower salt sensitivity in electrolyte media compared with unfilled gels.     

Antistatic performance and morphological observation of ternary blends of poly(ethylene terephthalate), poly(ether esteramide), and Na-neutralized poly(ethylene-co-methacrylic acid) copolymers

Blends of poly(ethylene terephthalate) (PET) and poly(ether esteramide) (PEEA), which is known as an ion conductive polymer, were prepared by melt mixing using a twin screw extruder. Antistatic performance of the molded plaques of the binary blends was investigated and the effects of adding sodium ionomer, Na-neutralized poly(ethylene-co-methacrylic acid) (E/MAA) Copolymers, in comparison with NaI, were also investigated. We found Na-neutralized E/MAA significantly improved static dissipation performance when blended with above PET/PEEA system whereas NaI was only effective when PEEA amount was larger than 25 wt%. Morphological study of these ternary blends system was conducted by using TEM and it was observed that PEEA domain formed platelet structure in PET matrix when PEEA content was 30%. The domain shape changed from sphere particle to platelet structure via string shape with the increase of PEEA content. And the thickness of the PEEA layers was confirmed as thin as 10 nm. Specific interaction between PEEA and Na-neutralized E/MAA was found by TEM. The Na-neutralized E/MAA domain was encapsulated by PEEA, which could increase the surface area of PEEA in PET matrix. This encapsulation effect explains the unexpected synergy for the static dissipation performance on addition of Na-neutralized E/MAA to PET/PEEA blends.     

Poly(ethylene glycol)/poly(2-acrylamido-2-methyl-1-propane sulfonic acid) gel electrolytes: a detailed investigation of their conductivity and characterization

Poly(ethylene glycol)/poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PEG/PAMPS) with a transparent appearance were prepared in the presence of ammonium persulfate (APS) as an initiator at 70 °C for 24 h. PEG/PAMPS-based polymer gel electrolytes in a motionless and uniform state were obtained by adding the required amount of liquid electrolytes to a dry PEG/PAMPS polymer. Liquid electrolytes include organic solvents with high boiling points (-1-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL)) and a redox couple (alkali metal iodide salt/iodine). The optimized conditions for PEG/PAMPS-based gel electrolytes based on the salt type, the concentration of alkali metal iodide salt/iodine, and solvent volume ratio were determined to be NaI, 0.4 M NaI/0.04 M I₂, and NMP:GBL (7:3, v/v), respectively. The highest ionic conductivity and the liquid electrolyte absorbency were 2.58 mS cm^?1 and 3.6 g g^?1 at 25 °C, respectively. The ion transport mechanism in both the polymer gel electrolytes and liquid electrolytes is investigated extensively, and their best fits with respect to the temperature dependence of the ionic conductivity are determined with the Arrhenius equation.     

Solid electrolyte membranes from semi-interpenetrating polymer networks of PEG-grafted polymethacrylates and poly(methyl methacrylate)

Solid polymer electrolyte membranes were prepared as semi-interpenetrating networks by photo-induced polymerization of mixtures of poly(ethylene glycol) (PEG) methacrylate macromonomers in the presence of poly(methyl methacrylate) (PMMA) and lithium bis(trifluoromethanesulfonyl)imide salt. The composition of the membranes was varied with respect to the PMMA content, the degree of cross-linking, and the salt concentration. Infrared analysis of the membranes indicated that the lithium ions were coordinated by the PEG side chains. Calorimetry results showed a single glass transition for the blend membranes. However, dynamic mechanical measurements, as well as a closer analysis of the calorimetry data, revealed that the blends were heterogeneous systems. The ionic conductivity of the membranes increased with the content of PEG-grafted polymethacrylate, and was found to exceed 10^− 5 S cm^− 1 at 30 °C for membranes containing more than 85 wt.% of this component in the polymer blend.