Structure and ionic interactions of organic-inorganic composite polymer electrolytes studied by solid-state NMR and Raman spectroscopy

Solid-state NMR studies of composite polymer electrolytes are reported. The materials consist of polyethylene oxide and an organic inorganic composite, together with a lithium salt, and are candidates for electrolytes in solid-state lithium ion batteries. Silicon and aluminum MAS and multiple quantum MAS are used to characterize the network character of the organic-inorganic composite, and spin diffusion measurements are used to determine the nanostructure of the polymer/composite blending. Multiple quantum spin counting is used to measure the ion aggregation. The NMR results are supported by Raman spectra, calorimetry, and impedance spectroscopy. From these experiments it is concluded that the composite suppresses polymer crystallization without suppressing its local mobility, and also suppresses the tendency for the ions to aggregate. This polymer composite thus appears very promising for application in lithium ion batteries.     

Ionic interactions in solutions of electrolytes as studied by ultra-violet spectroscopy

Spectrophotometric evidence for the formation of contact ion-pairs in solutions of tetra-alkylammonium iodides in certain solvents of poor ion-solvating power, such as carbon tetrachloride, is presented.

Since the band ascribed to contact ion-pairs is not detected for solutions in other solvents, such as chloroform, it is concluded that the ion-pairs detectable by other techniques in such solvents are separated by solvent molecules.     

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.     

Investigation of transport properties of chitosan-based electrolytes utilizing impedance spectroscopy

A method based on impedance spectroscopy has been utilized to obtain values of transport parameters such as number density, mobility and diffusion coefficient of mobile ions of solid polymer electrolytes (SPEs). SPE membranes consisting of chitosan and various amounts of oxalic acid (C₂O₄H₂) from 10 to 50 wt% have been prepared by the solution casting method. The Nyquist plots of all electrolytes have been fitted using the impedance equations based on equivalent circuits, and the parameters involved have been evaluated by trial and error. Number density, mobility and diffusion coefficient of mobile ions were calculated based on the parameters obtained. The values obtained from the proposed electrical impedance spectroscopy method are in reasonable agreement with those calculated using the percentage of mobile ions obtained from Fourier transform infrared (FTIR) measurements. The results were further compared with the results obtained using broadband dielectric response or Bandara-Mellander approach. The findings were confirmed by repeating the measurements and calculations on a glycerol-chitosan-oxalic acid-based electrolyte.     

Probing microstructure of polymer electrolyte-salt complex through impedance spectroscopy

In study of polymer-salt complexes usually one is interested in the dc conductivity, which can be extracted from impedance spectroscopy. However, impedance spectroscopy yields a host of additional information, for example, frequency variation of the measured admittance or impedance, nature of the Cole-Cole plot and dielectric function. Proper analysis of this information reveals details of the microstructure and transport processes in the sample. This in turn, will lead to development of better solid electrolytes with tailor-made properties. The polymer electrolyte PEO-NH₄ClO₄ shows an interesting variation in its properties in two different regimes, (1) where salt concentration is below ∼ 19 wt.% and (2) above this concentration. In the present paper we suggest an equivalent circuit incorporating a constant phase element (CPE), which reproduces the complex admittance behavior at different salt fractions. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

High pressure behaviour of KHSO4 studied by electrical impedance spectroscopy

Measurements of the electrical conductivity were performed in KHSO₄ at pressures between 0.5 and 2.5 GPa and in the temperature range 120-350 °C by the use of the impedance spectroscopy. The temperatures of the α-β phase transition (T_Tr) and of the melting (T_m), determined from the Arrhenius plots ln(σT) vs. 1/T, increase with pressure up to 1.5 GPa having dT/dP∼+45 K/GPa. Above the pressure 1.5 GPa, the pressure dependencies of T_Tr and T_m are negative dT/dP∼−45 K/GPa. At pressures above 0.5 GPa, the reversible decomposition of KHSO₄ into K₃H(SO₄)₂+H₂SO₄ (and probably into K₅H₃(SO₄)₄+H₂SO₄) affects the electrical conductivity of KHSO₄, with the typical values of the protonic electrical conductivity, c. 10⁻¹ S/cm at 2.5 GPa.     

Nanocomposite polymer electrolytes

The present effort reviews the state-of-the-art trends in respect of composite polymer electrolytes (CPEs) which are nowadays revolutionizing the modern approach towards energy storage and power supply gadgets. This evaluation mainly encompasses a series of systems based on polymer hosts such as poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP), poly(vinylidene fluoride) (PVDF), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), and polyvinylchloride (PVC) developed and analyzed so far apart from certain nanofiller incorporated composite polymer electrolytes being used in conjunction with well-suited electrodes owing to their practical significance in several advanced types of power sources including hybrid electric vehicles. The emerging nanoscale techniques have by now led the market to appreciate the application potential of nanostructured inorganic and organic materials so as to realize enhanced efficiencies of batteries thereby providing one of the most promising energy storage devices as well.     

Vibrational and impedance spectroscopic analysis of poly(vinyl alcohol)-based solid polymer electrolytes

Solid polymer electrolytes based on poly(vinyl alcohol) (PVA) doped with NH₄Br have been prepared by the solution-casting method. The complex formation between the polymer and the salt has been confirmed by Fourier transform infrared spectroscopy. The highest conductivity at 303 K has been found to be of the order of 10⁻⁴ Scm⁻¹ for 25 mol% NH₄Br-doped PVA system. The ionic transference number of polymer electrolyte has been estimated by Wagner’s polarization method, and the results reveal that the conducting species are predominantly ions. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Local electrical overstressing in polymer dielectrics

Using a spherical concentric capacitor as a microspike model, the electric field distribution in a polymer dielectric material with shallow and deep electron traps is investigated. It is established that in the course of field emission from microspikes on the electrode and space charge accumulation on the traps, the values of coefficient of electric overstresses depend on temperature, injection barrier height, and trap concentration and depth in the polymer material. The behavior of this coefficient is characterized as a function of the mean field strength. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 3–9, December, 2008.     

Evidence of ion pair breaking by dispersed polymer in polymer gel electrolytes

Non-aqueous polymer gel electrolytes containing trifluoromethanesulfonic acid (HCF₃SO₃) and polyethylene oxide (PEO) as the gelling polymer has been studied. The increase in conductivity observed with the addition of PEO to liquid electrolytes has been explained to be due to the breaking of ion aggregates present in electrolytes at higher acid concentrations. The increase in free H⁺ ion concentration upon breaking of ion aggregates has also been observed in pH measurements and viscosity of gel electrolytes has been found to increase with PEO addition. Polymer gel electrolytes containing dimethylacetamide (DMA) have σ ∼ 10⁻² S/cm at room temperature and are stable over −50 to 125 °C range of temperature. Gels based on propylene carbonate (PC) and ethylene carbonate (EC) are stable in the −50 to 40 °C temperature range and loose their gelling nature above 40 °C.     

Evidence of ion pair breaking by dispersed polymer in polymer gel electrolytes

Non-aqueous polymer gel electrolytes containing trifluoromethanesulfonic acid (HCF₃SO₃) and polyethylene oxide (PEO) as the gelling polymer has been studied. The increase in conductivity observed with the addition of PEO to liquid electrolytes has been explained to be due to the breaking of ion aggregates present in electrolytes at higher acid concentrations. The increase in free H⁺ ion concentration upon breaking of ion aggregates has also been observed in pH measurements and viscosity of gel electrolytes has been found to increase with PEO addition. Polymer gel electrolytes containing dimethylacetamide (DMA) have σ ∼ 10⁻² S/cm at room temperature and are stable over −50 to 125 °C range of temperature. Gels based on propylene carbonate (PC) and ethylene carbonate (EC) are stable in the −50 to 40 °C temperature range and loose their gelling nature above 40 °C.     

Impedance spectra of polymer electrolytes

The authors present a phenomenological view on dielectric relaxation in polymer electrolytes. Polymer electrolytes are seen as molecular mixtures of an organic polymer and an inorganic salt. The following is based on systems with high molar mass poly(ethylene oxide) (PEO) and epoxidized natural rubber with 25 mol% of epoxide content (ENR-25) filled with lithium perchlorate (LiClO₄). Dielectric properties of these systems have been studied as a function of salt content at room temperature. Additionally, properties of neat low molar mass PEO were studied as function of temperature. Relaxation-coined dielectric behavior rules the system with PEO in the frequency that ranged up to 10⁶ Hz. Imaginary parts of impedance, tangent loss, and electric modulus spectra show distribution of relaxation times. Comparison of tangent loss (tan δ) spectra and imaginary part of electric modulus (M″) spectra reveals that localized motion dominates long-range motion of dipoles in the low-frequency range. However, discrepancy between them decreases with growing salt content. Scaling of tan δ spectra demonstrates that distribution of relaxation times does not depend on salt content in the range of low frequencies. The ENR-25 system exhibits solely relaxation like a macroscopic dipole. In conclusion, the system with PEO is characterized by individual relaxation of well-interacting dipoles, whereas the system based on ENR-25 is coined by immobilized dipoles that lead in the state of high-salt content to the relaxation behavior of a macroscopic dipole.     

Interionic potential energy studied by far-infrared spectroscopy

Ionic potential models for tetra-alkylammonium halides are proposed, the repulsive energy being evaluated from crystal properties. By assuming a CsCl type structure, such potentials give a qualitative agreement with far-infrared (FIR) spectroscopic data (lattice bands and ion-pair vibration in solution) for a series of salts. For Pr₄NBr, the true structure is known and a more realistic potential has been elaborated. It is shown that the ionic potential is largely determined by the number of first neighbours and the shortest anion-cation distance in the solid. A possible way to estimate the repulsive energy for any R₄NX salt is suggested by using ion-pair dipole moment and vibration frequency data.     

Bromine metallization studied by X-ray absorption spectroscopy

The experimental data carried out by M?ssbauer and magnetic resonances investigations of the structural phase transitions in K₂ZnCl₄ crystals are discussed by a simple electrostatic model, calculating, the lattice contributions to the local electric potential V(r), electric field intensity E(r) and electric field gradient tensor, (r) and taking into account both the fractional electric point charges and rigid lattice approximations. The validity of the model is proved by a good fit of the computing results and experimental data of quadrupole splitting parameters at K sites obtained by ³⁹K-NMR methods in high temperature incommensurate phase ( Pnam symmetry). The experimental results obtained by M?ssbauer and EPR methods in commensurate phase (Pna2₁ symmetry) of iron and copper doped K₂ZnCl₄ crystals are explained by relaxing the rigid lattice approximation. The insertion of probe ions appear to be done on not-exactly-Zn²⁺ site. Received 3 February 1999 and Received in final form 4 May 1999     

Polyphosphazene based composite polymer electrolytes

Composite salt-in-polymer electrolyte membranes were prepared from poly[(bis(2-methoxyethyl)amino)_1−x(n-propylamino)_x-phosphazene] (BMEAP) with dissolved LiCF₃SO₃ and dispersed Al₂O₃ nanoparticles (40 nm). Membranes with good mechanical stability were obtained. Low ionic conductivities were found in particle free membranes with maximum conductivities at 10 wt.% LiCF₃SO₃ ranging from 3.1 × 10^− 7 S/cm at 30 °C to 1.8 × 10^− 5 S/cm at 90 °C. For the composite membranes, addition of 2 wt.% Al₂O₃ nanoparticles leads to a steep increase of the conductivity by almost two orders of magnitude as compared to the homogeneous membranes. The highest room temperature conductivity for the investigated BMEAP–LiCF₃SO₃–Al₂O₃ composite systems was 10^− 5 S/cm.