On dielectrics of polymer electrolytes studied by impedance spectroscopy

We present a phenomenological view on dielectric relaxation in polymer electrolytes in the frequency range where conductivity is independent of frequency. Polymer electrolytes are seen as molecular mixtures of an organic polymer and an inorganic salt. The discussion applies also to ionic liquids. The following is based on systems with poly(ethylene oxide) (PEO) comprising the lithium perchlorate salt (LiClO₄) and also pure low-molecular PEO. In those systems, dipole-dipole interactions form an association/dissociation equilibrium which rules properties of the system in the low-frequency region. It turns out that effective concentration, c _S, of relaxing species provides a suitable variable for discussing electrochemical behavior of the electrolytes. Quantity c _S is proportional to the ratio of DC conductivity and mobility. Polymer salt mixtures form weak electrolytes. However, diffusion coefficient and corresponding molar conductivity display the typical (c _S)^1/2 dependence as well known from strong electrolytes, due to the low effective concentration c _S.     

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.     

Preparation and ionic conductivity of composite polymer electrolytes based on hyperbranched star polymer

Hyperbranched star polymer HBPS-(PPEGMA) _x was synthesized by atom transfer radical polymerization (ATRP) using hyperbranched polystyrene (HBPS) as macroinitiator and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as monomer. The structure of the prepared hyperbranched star polymer was characterized by ¹H NMR, ATR-FTIR, and GPC. Polymer electrolytes based on HBPS-(PPEGMA) _x , lithium salt, and/or nano-TiO₂ were prepared. The influences of lithium salt concentration and type, nano-TiO₂ content, and size on ionic conductivity of the obtained polymer electrolytes were investigated. The results showed that the low crystallinity of the prepared polymer electrolyte was caused by the interaction between lithium salt and polymer. The addition of TiO₂ into HBPS-(PPEGMA) _x /LiTFSI improved the ionic conductivity at low temperature. The prepared composite polymer electrolyte showed the highest ionic conductivity of 9?×?10^?5 S cm^?1 at 30 °C when the content of TiO₂ was 15 wt% and the size of TiO₂ was 20 nm.     

Molecular dynamics of polycrystalline cellobiose studied by solid-state NMR

Molecular motions of polycrystalline cellobiose have been investigated by measuring proton spin–lattice relaxation times, T₁ and T_1ρ, and the second moment, M₂, in both protonated and D₂O exchanged forms over the temperature range 120–380 K. T₁ relaxation is dominated by the motions of hydroxyl groups between 150 and 380 K, characterised by an activation energy of about 8.74 kJ/mol, whereas T_1ρ relaxation is driven by the motions of the same groups between 120 and 300 K. T_1ρ results suggest that hydroxyl groups have a distribution of dynamics. Motion of methylene groups was detected in the second-moment experiments at about 350 K, characterised by activation energy of about 40 kJ/mol. Consideration of the calculated and observed rigid-lattice second moments suggests that the reported X-ray data are incorrect for the inter-proton distance on C6′. ¹³C CPMAS spectra of both protonated and deuterated cellobiose have also been measured. Spectra of the deuterated material showed the existence of a second crystalline form in addition to the normal form.     

Solid-state photodimerization of 9-methylanthracene as studied by solid-state NMR

The locus of the photodimerization reaction of 9-methylanthracene in the crystal was examined by high-resolution solid-state NMR techniques. Examination of the spectra of the products showed that only the trans dimer is formed by the solid state photodimerization, while both trans and cis dimers are formed by the photodimerization in benzene solution. The T₁ relaxation curves for the monomer and the dimer at various exposure times were separately observed via well-resolved peaks. The two T₁ curves exhibit characteristic features for relaxation of a weakly coupled two-spin system. By analyzing the T₁ curves, the spin diffusion rates between the monomer and the dimer and the fraction of the dimer were obtained for various exposure times. From the result, the maximum domain size of the minor component during the photodimerization process was estimated to be ca. 0.3 μm. The heterogeneous domain structure generated by the photodimerization indicates that the reaction takes place at defects of the crystal in the monomer.     

Molecular dynamics of poly(L-lactide) biopolymer studied by wide-line solid-state 1H and 2H NMR spectroscopy

The molecular dynamics of poly(L-lactide) (PLLA) biopolymer was characterized through analyses of 1H and 2H NMR line-shapes and spin-lattice relaxation times at different temperatures. At low temperatures (e.g. 90 K), the methyl group rotation is dominant leading to a significant reduction in the proton second moment. Fast methyl group reorientation occurs at ca. 130 K. In additional to the fast methyl group rotation, hydroxyl groups start to reorient as the temperature increases further, eventually leading to the breakdown of the segments of the biopolymer chains above its glass transition temperature Tg of 323 K. The analyses of the 2H NMR line-shapes indicate that both the methyl and hydroxyl reorientations can be described by the so-called cone model, in which the former has three equilibrium positions with theta(C-D) = 70.5 degrees and phi = 120 degrees while the latter one exhibits two equilibrium positions with theta(O-D) = 78 degrees and phi = 180 degrees .     

The transformation of mackinawite into greigite studied by Raman spectroscopy

In this study, Raman spectroscopy was used to precisely understand the mechanisms of oxidation of mackinawite (FeS). Two experimental conditions were considered: (1) oxidation in air at room temperature and (2) oxidation in acidic anoxic solutions at 80 °C. In both cases, the oxidation process began by the in situ oxidation of Fe(II) cations inside the crystal structure of mackinawite and led to Fe(III)‐containing mackinawite, Fe^II_1−3xFe^III_2xS. The oxidation in air finally led to Fe(III) oxyhydroxides and elemental sulfur α‐S₈, but greigite (Fe₃S₄) was observed as an intermediate compound. In anoxic acidic solutions, the product of the oxidation was proved to depend on the Fe/S concentration ratio. For Fe/S = 3/4, greigite was the only product obtained, and this allowed us to determine unambiguously the Raman spectrum of this compound. Copyright © 2010 John Wiley & Sons, Ltd.     

Recrystallization behavior of high-fluence N-implanted GaAs studied by Raman spectroscopy

Raman spectroscopy was used to study the evolution of host lattice recrystallization in high-fluence N⁺-implanted GaAs. A high-fluence of N⁺ ions (>10¹⁵ cm⁻²) was introduced into semi-insulating GaAs by the combinatorial implantation method. Subsequent thermal annealing at 800 °C was carried out to re-grow the implantation-induced amorphous layers. The dependence of Raman parameters on N contents was systematically observed for each recrystallized cell. The volume of the newly formed crystallites with original orientation decreases with increasing fluences, whereas that of crystallites of other orientations increases after high-fluence implantation and annealing. The correlation length L, representing the size of crystalline regions with preserved translational symmetry, was determined by fitting the LO phonon signal with spatial correlation model. For 10¹⁶ cm⁻² implantation, the recrystallized layer consists of nano-meter-sized crystallites (∼30 nm). The dimension of the recrystallized crystallites decreases with increasing N⁺ fluences, in good agreement with the model.     

Monitoring the evolution of crystallization processes by in-situ solid-state NMR spectroscopy

Crystallization processes play a crucial role in many aspects of biological and physical sciences. Progress in deepening our fundamental understanding of such processes relies, to a large extent, on the development and application of new experimental strategies that allow direct in-situ monitoring of the process. In this paper, we give an overview of an in-situ solid-state NMR strategy that we have developed in recent years for monitoring the time-evolution of different polymorphic forms (or other solid forms) that arise as the function of time during crystallization from solution. The background to the strategy is described and several examples of the application of the technique are highlighted, focusing on both the evolution of different polymorphs during crystallization and the discovery of new polymorphs.     

Ferroelastic phase transition in CaCl2 studied by Raman spectroscopy

CaCl₂ undergoes a second-order proper ferroelastic phase transition from the tetragonal rutile type to the orthorhombic calcium-chloride type structure atT _c 490 K. The transition is of the optical type and induced by an order parameter ofB _1g symmetry. An underdamped soft mode exists above and belowT _c , the frequency and intensity of which have been measured by Raman spectroscopy. Due to a strong coupling to strain the softening is incomplete and a transverse acoustical mode is predicted to become soft. The frequency of the optical soft mode, _s, exhibits a classical Landau behavior in a remarkably large temperature range. The unusual value of the ratio of _s ² / below and aboveT _c of about –6.5 can be accounted for by appropriate terms of the thermodynamical potential. The Raman active hard modes show no significant anomaly atT _c .     

Influence of plasticizer on ionic conductivity of PVC-PBMA polymer electrolytes

Plasticized polymer electrolytes comprising of ethylene carbonate as the plasticizing agent in poly (vinyl chloride) [PVC]–poly (butyl methacrylate) [PBMA] blended polymer electrolytes were prepared by solution casting technique. Complex formation, structural elucidation, conductivity, dielectric parameters (?′, ?″, M′, and M″), thermal stability, and surface morphology are brought out from FTIR, XRD, ac impedance analysis, dielectric studies, thermogravimetry/differential thermal analysis, and scanning electron microscopic studies, respectively. Polymer electrolytes are found to exhibit higher ionic conductivity at higher concentration of plasticizer at the cost of their mechanical stability. Conductivity of 1.879 × 10^?4 S cm^?1 is exhibited by the polymer electrolyte consisting of 69% of plasticizer with appreciable thermal stability up to 523 K. Temperature and frequency dependence of conductivity is found to follow Vogel Tammann Fulcher relation and Jonscher power law, respectively. Real and imaginary parts of dielectric constants are found to decrease with increase in frequency which could be due to the electrode polarization effect.     

A computer simulation study of ionic conductivity in polymer electrolytes

In this paper we present a computer simulation study of ionic conductivity in solid polymeric electrolytes. The multiphase nature of the material is taken into account. The polymer is represented by a regular lattice whose sites represent either crystalline or amorphous regions with the charge carrier performing a random walk. Different waiting times are assigned to sites corresponding to the different phases. A random walk (RW) is used to calculate the conductivity through the Nernst-Einstein relation. Our walk algorithm takes into account the reorganization of the different phases over time scales comparable to time scales for the conduction process. This is a characteristic feature of the polymer network. The qualitative nature of the variation of conductivity with salt concentration agrees with the experimental values for PEO-NH₄I and PEO-NH₄SCN. The average jump distance estimated from our work is consistent with the reported bond lengths for such polymers.     

Effect of branching in base polymer on ionic conductivity in hyperbranched polymer electrolytes

Novel hyperbranched polymer, poly[bis(diethylene glycol)benzoate] capped with a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group (poly-Bz1a), was prepared, and its polymer electrolyte with LiN(CF₃SO₂)₂, poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte, was all evaluated in thermal properties, ionic conductivity, and electrochemical stability window. The poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte exhibited higher ionic conductivity compared with a polymer electrolyte based on poly[bis(diethylene glycol)benzoate] capped with an acetyl group (poly-Ac1a), and the ionic conductivity of poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte was to be 7×10⁻⁴ S cm⁻¹ at 80 °C and 1×10⁻⁶ S cm⁻¹ at 30 °C, respectively. The existence of a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group as a branching unit present at ends in the base polymer improved significantly ionic conductivity of the hyperbranched polymer electrolytes. The polymer electrolyte exhibited the electrochemical stability window of 4.2 V at 70 °C and was stable until 300 °C.     

Sensitivity and resolution enhancement in solid-state NMR spectroscopy of bicelles

Magnetically aligned bicelles are becoming attractive model membranes to investigate the structure, dynamics, geometry, and interaction of membrane-associated peptides and proteins using solution- and solid-state NMR experiments. Recent studies have shown that bicelles are more suitable than mechanically aligned bilayers for multidimensional solid-state NMR experiments. In this work, we describe experimental aspects of the natural abundance (13)C and (14)N NMR spectroscopy of DMPC/DHPC bicelles. In particular, approaches to enhance the sensitivity and resolution and to quantify radio-frequency heating effects are presented. Sensitivity of (13)C detection using single pulse excitation, conventional cross-polarization (CP), ramp-CP, and NOE techniques are compared. Our results suggest that the proton decoupling efficiency of the FLOPSY pulse sequence is better than that of continuous wave decoupling, TPPM, SPINAL, and WALTZ sequences. A simple method of monitoring the water proton chemical shift is demonstrated for the measurement of sample temperature and calibration of the radio-frequency-induced heating in the sample. The possibility of using (14)N experiments on bicelles is also discussed.     

Decoupling of ionic transport from segmental relaxation in polymer electrolytes

We present detailed studies of the relationship between ionic conductivity and segmental relaxation in polymer electrolytes. The analysis shows that the ionic conductivity can be decoupled from segmental dynamics and the strength of the decoupling correlates with the fragility but not with the glass transition temperature. These results call for a revision of the current picture of ionic transport in polymer electrolytes. We relate the observed decoupling phenomenon to frustration in packing of rigid polymers, where the loose local structure is also responsible for the increase in their fragility.