Studies of solvent effect on the conductivity of 2‐mercaptopyridine‐doped solid polymer blend electrolytes and its application in dye‐sensitized solar cells

Solvents and electrolytes play an important role in the fabrication of dye‐sensitized solar cells (DSSCs). We have studied the poly(ethylene oxide)‐poly(methyl methacrylate)‐KI‐I₂ (PEO‐PMMA‐KI‐I₂) polymer blend electrolytes prepared with different wt % of the 2‐mercaptopyridine by solution casting method. The polymer electrolyte films were characterized by the FTIR, X‐ray diffraction, electrochemical impedance and dielectric studies. FTIR spectra revealed complex formation between the PEO‐PMMA‐KI‐I₂ and 2‐mercaptopyrindine. Ionic conductivity data revealed that 30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂ electrolyte can show higher conductivity (1.55 × 10^?5 S cm^?1) than the other compositions (20, 40, and 50%). The effect of solvent on the conductivity and dielectric of solid polymer electrolytes was studied for the best composition (30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂) electrolyte using various organic solvents such as acetonitrile, N,N‐dimethylformamide, 2‐butanone, chlorobenzene, dimethylsulfoxide, and isopropanol. We found that ac‐conductivity and dielectric constant are higher for the polymer electrolytes processed from N,N‐dimethylformamide. This observation revealed that the conductivity of the solid polymer electrolytes is dependent on the solvent used for processing and the dielectric constant of the film. The photo‐conversion efficiency of dye‐sensitized solar cells fabricated using the optimized polymer electrolytes was 3.0% under an illumination of 100 mW cm^?2. The study suggests that N,N‐dimethylformamide is a good solvent for the polymer electrolyte processing due to higher ac‐conductivity beneficial for the electrochemical device applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42489.     

Impedance of interface between PEO:LiTFSI polymer electrolyte and blocking electrodes

The impedance spectra of electrolytes comprising poly(ethylene oxide) (PEO) with LiN(CF₃SO₂)₂ (LiTFSI) salt were measured for a wide range of concentration of salt in polymer electrolyte (from pure PEO to molar ratio of 1:1 EO:Li) and in various states (amorphous and semicrystalline). The measurements were performed on membranes placed between gold-plated stainless steel electrodes. Investigations of crystallization and melting with simultaneous observations in a polarizing microscope were performed between glass plates covered with film of indium tin oxide. The impedance data were analyzed by least squares fitting of equivalent circuit. Two different equivalent circuits were proposed for modeling of interfacial impedance for electrolytes with low and high concentration of salt, respectively. The decrease of the contact area due to the increase of stiffness of electrolyte and changes of electrical properties of the interfacial layer due to the presence of crystalline lamellae were identified as the major causes for changes of impedance of the interface layer taking place during crystallization.     

Effects of amorphous silica nanoparticles and polymer blend compositions on the structural,thermal and dielectric properties of PEO–PMMA blend based polymer nanocomposites

The polymer nanocomposite (PNC) films consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrices dispersed with nanoparticles of amorphous silica (SiO₂) have been prepared by solution-cast method followed by melt-press technique. Effects of SiO₂ concentration (x?=?0, 1, 3 and 5 wt%) and PEO–PMMA blend compositional ratios (PEO:PMMA?=?75:25, 50:50, and 25:75 wt%) on the surface morphology, crystalline phase, polymer-polymer and polymer-nanoparticle interactions, melting phase transition temperature, dielectric permittivity, electrical conductivity, electric modulus and the impedance properties of the PNC films have been investigated. The crystalline phase of the PNC films decreases with the increase of PMMA contents which also vary anomalously with the increase of SiO₂ concentration in the films. The melting phase transition temperature and polymer-nanoparticle interactions significantly change with the variation in the compositional ratio of the blend polymers in the PNC films. It is observed that the effect of SiO₂ on the dielectric and electrical properties of these PNCs vary greatly with change in the compositional ratio of PEO and PMMA in the blends. The dielectric relaxation process of these films confirm that the polymers cooperative chain segmental dynamics becomes significantly slow when merely 1 wt% SiO₂ nanoparticles are dispersed in the polymer blend matrix.     

Structural and dielectric studies of amorphous and semicrystalline polymers blend‐based nanocomposite electrolytes

The solid polymeric nanocomposite electrolyte (SPNE) films based on the blend of amorphous poly(methyl methacrylate) (PMMA) and semicrystalline poly(ethylene oxide) (PEO) (PMMA:PEO = 80:20 wt %) doped with lithium perchlorate (LiClO₄) salt and montmorillonite (MMT) clay nanofiller were prepared by classical solution cast, ultrasonic assisted solution cast and ultrasonication along with microwave irradiated solution cast followed by melt‐pressing methods. The X‐ray diffraction study of these electrolytes revealed the amorphous behavior with intercalated MMT structures. The suppressed crystallinity of PEO in the blend electrolyte complexes confirmed the existence of single discrete PEO chains confined within the PMMA domains. The dielectric relaxation spectroscopy of these materials was performed over the frequency range 20 Hz to 1 MHz, at ambient temperature. The presence of a singular relaxation peak in the loss tangent and electric modulus spectra of these electrolytes confirms a coupled cooperative chain segmental dynamics of the blend polymer owing to their miscible amorphous morphology. The behavior of transient complexes formed between the polymers functional groups, lithium cations and the intercalated MMT nanoplatelets was explored. The ambient temperature ionic conductivity of these electrolytes depends on the structural dynamics and the sample preparation methods. It is revealed that the presence of PEO in the PMMA matrix mainly governs the structural, dielectric, and ionic properties of these SPNE films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41311.     

Poly (ethylene oxide) (PEO) influence on mechanical,thermal, and degradation properties of PLA/PBSeT blends

Poly (lactic acid) (PLA) is an important biodegradable plastic with unique properties. However, its widespread application is hindered by its low miscibility and suboptimal degradation properties. To overcome these limitations, we investigated the mechanical, thermal, and degradation properties of PLA and poly (butylene sebacate-co-terephthalate) (PBSeT) blends in the presence of poly (ethylene oxide) (PEO). Specifically, this study aimed to identify the effects of PEO as a compatibilizer and hydrolysis accelerator in PLA/PBSeT blends. PLA (80%) and PBSeT (20%) were melt blended with various PEO contents (2–10 phr), and their mechanical, thermal, and hydrolytic properties were analyzed. All PEO-treated blends exhibited a higher elongation at break than that of the control sample, and the tensile strength was slightly reduced. In the PEO 10% sample, the elongation at break increased to 800% of that of the control sample. Differential scanning chromatography (DSC) analysis confirmed that when PEO was added to the PLA/PBSeT blends, the two glass transition temperatures (T_g) narrowed, resulting in improved miscibility of PLA and PBSeT. In addition, the hydrolytic degradation of the PLA/PBSeT/PEO blend accelerated as the PEO content increased. It was confirmed that PEO can act as a compatibilizer and hydrolysis-accelerating agent for PLA/PBSeT blends.     

Effects of frequency,molecular weight and thermal oxidation on the dynamic mechanical response of poly (ethylene oxide)

The technique of dynamic mechanical thermal analysis (DMTA), operated in the dual cantilever mode, was used to characterize the effects of frequency, crystallinity, molecular weight (MW) and the extent of thermal oxidation on the dynamic mechanical response of poly(ethylene oxide) (PEO). The glass transition temperature (T_g) of PEO (MW = 9 × 10⁵ Dalton) was found to be ?44°C. For PEO (MW = 1 × 10⁵ Dalton) the T_g is ?39°C and this value increases by 2–9°C for every decade increase in the measuring frequency. Two minor, second-order transitions of PEO are also discernible at ?33 and 32°C. An inverse dependence of T_g on molecular weight was found in the molecular weight range studied and this is contrary to the Fox-Flory theory. It was also found that a partially crystalline sample is obtained despite very rapid quenching of PEO from the melt into liquid nitrogen. Thermal oxidation of PEO before processing leads to an increase in the amplitude of the loss tangent peak. This reflects the effect of oxidation products in restricting polymer crystallization and the subsequent increase in the amorphous fraction of the polymer. The position of the T_g peak in PEO remains reasonably fixed with progressive ageing and this was attributed to crosslinking having occurred in addition to chain scission during thermal oxidation.     

Morphology and photophysical properties of luminescent electrospun fibers prepared from diblock and triblock polyfluorene-<Emphasis Type="Italic">block</Emphasis>-Poly(2-vinylpyridine)/PEO blends

We successfully prepared luminescent electrospun (ES) fibers from the polymer blends of diblock poly[2,7-(9,9-dihexylfluorene)]-block-poly(2-vinylpyridine)(di-PFPVP) or triblock P2VP-b-PF-b-P2VP (tri-PFPVP) with polyethylene oxide (PEO) using a single-capillary spinneret. The morphology and photophysical properties of ES fibers were explored via the molecular architecture, solvent selectivity, and different molecular weights of PEO. The ES fibers had diameters around 400–800 nm using solvent of methanol (MeOH)/H₂O while those using CHCl₃ were around 1–3 μm, which was probably due to the difference on the solvent dielectric constant. Furthermore, the PF aggregated size and emission peak maximum in the ES fibers increased with enhancing the block copolymer composition using CHCl₃. However, an insignificant variation was observed using MeOH/H₂O. The larger PF aggregated size of the di-PFPVP/PEO blend ES fibers resulted in the red-shifting and broader emission peak, in comparison with that of the tri-PFPVP/PEO blend ES fibers. The efficient interaction of the PEO with the PVP block in two different block copolymers accounted for the above results. In the ES fibers using the low molecular weight of PEO (Mn~100 K), it exhibited a red-shifting on the PL spectra in comparison with the spin-coated films due to the geometrical confinement. Nevertheless, such confinement was probably significantly reduced using the high molecular weight PEO (Mn~2000 K) and thus an insignificant variation was found on the PL spectra. The present study demonstrated that their aggregate morphology and photophysical properties of ES fibers prepared from conjugated rod-coil block copolymer blends could be significantly tuned through polymer architecture, solvent selectivity, and copolymer composition.     

Hyperbranched Poly(Glycidol)-Grafted Silica Nanoparticles for Enhancing Li-Ion Conductivity of Poly(Ethylene Oxide)

Silica nanoparticles bearing hyperbranched polyglycidol (hbP) grafts are synthesized and blended with poly(ethylene oxide) (PEO) for the fabrication of composite solid polymer electrolytes (SPEs) for enhancing Li-ion conductivity. Different batches of hbPs are prepared, namely, the 5th, 6th, and 7th with increasing molecular weights using cationic ring-opening polymerization and grafted the hbPs onto the silica nanoparticles using quaternization reaction. The effect of end functionalization of hbP-grafted silica nanoparticles with a nitrile functional group (CN–hbP–SiO₂) on the ionic conductivity of the blends with PEO is further studied. High dipole moments indicate polar nature of nitriles and show high dielectric constants. Among all the hbPs, the 6th-batch CN–hbP–SiO₂ nanoparticles exhibit better ionic conductivity on blending with PEO showing ionic conductivity of 2.3 × 10⁻³ S cm⁻¹ at 80 °C. The blends show electrochemical stability up to 4.5 V versus lithium metal.     

Physical characterization and performance of iron polymer composites

The physical properties of poly(ethylene oxide) (PEO) composites containing natural iron oxides with different concentrations 2, 4, 6, 8, 10, 15, and 20% by weight were studied. Powder of iron oxides of 63-μm particle size was casted with PEO polymer. Absorption UV spectra were collected in the wavelength range 300–800 nm by using a spectrophotometer. The optical energy gap and energy tail widths of localized states of the prepared composites were determined from Urbach formula. The electrical properties were studied using AC impedance measurements performed at different temperatures and in frequency range 100 kHz to 1 MHz. Impedance, dielectric constant, dielectric loss, and AC-conductivity showed frequency and temperature dependence. The thermal conductivity of the composites was studied as a function of iron oxides concentration and in temperature range 20–50°C. It was found that the thermal conductivity of the composites increases with filler concentration and temperature. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Lithium/polymer electrolyte interfacial instability

The stability of evaporated lithium with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO) and oxyethylene-oxymethylene copolymer, doped with lithium perchlorate, in ultra-thin-film cells, was studied by impedance spectroscopy at room temperature. The formation and growth of a passivating film at the lithium/PEO interface has been observed, under open circuit conditions. The thickness of the passivating layer was estimated by assuming the dielectric constant of the interfacial product. A more extensive interfacial reaction was observed in the case of PPO. A very fast interfacial reaction was observed between lithium and amorphous copolymer.     

Analysis of the Structural Characterization,Electric Transport,and Dielectrical Relaxation Behavior of Ba0.97La0.02Ti0.95Nb0.04O3 Electronic Ceramic

Ba_0.97La_0.02Ti_0.95Nb_0.04O₃ polycrystalline sample was produced through molten-salt technique. The morphological, structural, impedance and optical properties were investigated by scanning electron microscope, X-ray powder diffraction (XRD), and ultraviolet–visible diffuse reflectance spectrophotometer, respectively. XRD pattern illustrate a single-pure phase of tetragonal perovskite structure with P4/mmm group space. No impurity was noticed for present ceramic. The optical band gap (E_g) values were calculated from the absorption spectra. Notwithstanding, electrical and dielectric properties were used to analyze the dielectric constant and loss, the modulus as well as dissipation factors as functions of both frequencies and d.c bias voltage for obtained sample. The frequency (f) dependence dielectric study shows that the value of dielectric constant is high at lower frequencies and decreases with increase in frequency. It is obvious to comprehend how to overwhelm the formation of inter-grain and intra-grain, and how to restrain the propagation of Ti species is an important challenge for the realization of an alternative “high-k gate dielectric” applications. Thus, some kind of semicircular arc caused by a variety of electrically active regions can originate from grains, grain boundaries, and electrode polarization effects. The modulus mechanism indicates the non-Debye type of conduction relaxation in the material, which is supported by impedance data.

     

Effect of polymer structure on the morphologies and dielectric properties of nanoporous polyimide films

Low dielectric constant polyimide (PI) films have potential applications in integrated circuit. In this study, poly(methyl methacrylate), poly(ethylene oxide), and polystyrene as thermally labile materials were used as templates to generate PI films with nanopores by first mixing the polymer templates with the precursor of PI, poly(amic acid), followed by imidization of poly(amic acid) together with degradation of the polymer templates. The sizes of the formed pores, the thermal and dielectric constant of the nanofoamed PI films were studied and compared in detail. It is concluded that the dielectric constant of PI films using poly(ethylene oxide) as pore template is more stable because of the formation of uniform pores which is from the great accordance of imidization temperature of poly(amic acid) with the degradation temperature of poly(ethylene oxide). But that using poly(methyl methacrylate) as pore template is frequency dependent as the influence of inhomogeneous pores and PMMA residue from incompletely degradation of poly(methyl methacrylate). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41480.     

Effect of nano-porous Al2O3 on thermal, dielectric and transport properties of the (PEO)9LiTFSI polymer electrolyte system

Thermal, electrical conductivity and dielectric relaxation measurements have been performed on (PEO)₉LiTFSI+10 wt.% Al₂O₃ nano-porous polymer electrolyte system. It is observed that the conductivity enhances substantially due to the presence of the filler particles with different surface groups. The highest enhancement is found for the filler particles with acidic groups followed by basic, neutral, and weakly acidic. The results reveal that the filler particles do not interact directly with poly(ethelene) oxide (PEO) chains indicating that the main chain dynamics governing the ionic transport has not significantly affected due to the filler. The results are consistent with the idea that the conductivity enhancement is due to the creation of additional sites and favourable conduction pathways for ionic transport through Lewis acid-base type interactions between the filler surface groups and the ionic species. This is reflected as an increase in the mobility rather than an increase in the number of charge carriers. A qualitative model has been proposed to explain the results.     

Dielectric properties and structures of melt‐compounded poly(ethylene oxide)–montmorillonite nanocomposites

The dielectric dispersion and relaxation process in melt‐compounded hot‐pressed poly(ethylene oxide) (PEO)–montmorillonite (MMT) clay nanocomposite films of 0–20 wt % MMT concentration were investigated over the frequency range 20 Hz to 1 MHz at ambient temperature. X‐ray diffraction study of the nanocomposites evidences that the PEO has been intercalated into the MMT interlayer galleries with a helical‐type multilayer structures, which results the formation of unique parallel plane PEO–MMT layered structures. The relaxation times corresponding to PEO chain segmental motion were determined from the loss peak frequencies of different dielectric formalisms and the same is used to explore the interactions compatibility between PEO molecules and the MMT nano platelets. It is revealed that the loading of only 1 wt % MMT in PEO matrix significantly increases the PEO chain segmental motion due to intercalation, which further varies anomalously with increase of MMT concentration. The real part of dielectric function at 1 MHz, relaxation time, and dc conductivity of these melt‐compounded nanocomposites were compared with the aqueous solution‐cast PEO–MMT films. Considering the comparative changes in the values of various dielectric parameters, the effect of synthesization route on the intercalated/exfoliated‐MMT structures and the PEO chain dynamics were discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dehydrochlorination of poly(vinyl chloride) modified with titanium dioxide/poly(ethylene oxide) based paint photocatalysts

The dehydrochlorination of poly(vinyl chloride) (PVC) film samples modified with titanium dioxide (TiO₂)/poly(ethylene oxide) (PEO) based paint photocatalysts [the addition of methyl linoleate (ML) or methyl oleate (MO)] was performed. After 24 h of UV photoirradiation, the sample with TiO₂/PEO showed that there existed a structure with the longest polyene length, whereas that with TiO₂/PEO/ML contained the most polyene structures. The chloroform‐soluble fraction of the sample with TiO₂/PEO contained a poly(vinyl alcohol) (PVA) structure instead of a polyene one and showed a novel method of PVA production via PVC photodegradation. The molecular weight curve of the fraction shifted slightly to a lower molecular weight compared to that without the photocatalyst; this showed that slight polymer chain scission occurred. The ¹H‐NMR and ¹³C‐NMR spectra showed that the content of PVA units was about 20%, and the PVA sequence was blocky. The fraction of the sample with TiO₂/PEO/ML contained the highest methyl group content; this showed that the branch degree was highest as was the polyene content. These highest contents were due to the existence of the grafted ML. Pyrolysis gas chromatography/mass spectroscopy measurements suggested that there existed more polyene and graft units in the chloroform‐insoluble fractions of the samples with TiO₂/PEO, TiO₂/PEO/ML, and TiO₂/PEO/MO, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40760.     

Enhancement of discharged energy density of poly(ethylene oxide) by soy protein isolate

Soy protein isolate (SPI) is used to modify energy storage performances of poly(ethylene oxide) (PEO). The pure PEO membranes are highly polar, but the extremely high energy loss led to very low discharged energy density for use. The addition of SPI in both high molecular weight PEO and low molecular weight PEO lead to greatly reduced polarization and stored energy density. However, it also largely reduces the current leakage and energy loss of the resulting membranes, leading to significantly enhanced discharged energy density. It is believed that the strong interactions between PEO and SPI are responsible for the energy storage properties aforementioned. Meanwhile, such interactions also result in a more brittle fracture behavior and reduced crystallinity of the PEO/SPI membranes. The enhanced discharged energy density and low energy loss suggest PEO/SPI membranes are promising dielectric materials for high efficiency energy storage applications where soluble and transient materials are desired. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45214.     

Studies of dielectric relaxation and a.c. conductivity in [(100−<Emphasis Type="Italic">x</Emphasis>)PEO + <Emphasis Type="Italic">x</Emphasis>NH<Subscript>4</Subscript>SCN]: Al-Zn ferrite nano composite polymer electrolyte

Present work deals with findings on dielectric behaviour and a.c. conduction in a ferrite doped polymer nano composite electrolyte system, namely [(100−x) PEO + xNH₄SCN]: ferrite. The formation of nano composite and structural behavior of electrolyte was studied by XRD and SEM images. The effect of salt and ferrite on conductivity behaviour of PEO based nano composite polymer electrolyte has been investigated by the impedance spectroscopy at room temperature. The variation of dielectric permittivity and dielectric loss with frequency was carried out at ambient temperature. The a.c. conductivity seems to follow the universal power law.     

New solid polymer electrolytes based on PEO/PAN hybrids

Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO₄ were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO‐based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO₄‐PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO₄‐PEO‐PAN hybrid polymer electrolyte was heated at 200°C under N₂, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1530–1540, 2006     

Compatibilizing effects of poly(styrene-graft-ethylene oxide) in blends of polystyrene and butyl acrylate polymers

The compatibilizing effect of poly(styrene-graft-ethylene oxide) in polystyrene (PS) blends with poly(n-butyl acrylate) (PBA) and poly(n-butyl acrylate-co-acrylic acid) (PBAAA) was investigated. No significant effects of the graft copolymer on the domain size were found in the PBA blends. By functionalizing PBA with acrylic acid, the average size of the polyacrylate domains was reduced considerably by the graft copolymer. Thermal and dynamic mechanical analysis of the PS/PBAAA blends revealed that the PBAAA glass transition temperature (T_g) decreased with increasing graft copolymer content. The effect of the graft copolymer in the PS/PBAAA blends can be explained by interactions across the interface due to the formation of hydrogen bonds between the poly(ethylene oxide) (PEO) side chains in the graft copolymer and the acrylic acid segments in the PBAAA phase. Hydrogen bonding was confirmed by IR analysis of binary blends of PEO and PBAAA. Partial miscibility in the PEO/PBAAA blends was indicated by a PEO melting point depression and by a T_g reduction of the PBAAA phase. The thermal properties of the PEO/PBA blends indicated only very limited miscibility. © 1996 John Wiley & Sons, Inc.     

Oxygen and carbon dioxide permeability of EAA/PEO blends and microlayers

The goal of this study was to broaden the spectrum of gas permeability and selectivity characteristics of poly(ethylene‐co‐acrylic acid) (EAA) by combining it with poly(ethylene oxide) (PEO), which has a high selectivity for CO₂. To obtain films that differed substantially in their solid state morphologies, EAA was combined with PEO as melt blends and as coextruded films with many alternating, continuous microlayers of EAA and PEO. The solid state structure and thermal behavior were characterized and the permeability to O₂ and CO₂ was measured at 23°C. When the PEO was dispersed as small domains, the particles were too numerous for most of them to contain a heterogeneity that was sufficiently active to nucleate crystallization at the normal T_c. The rubbery, amorphous nature of the PEO domains enhanced the gas permeability of the melt blends. In contrast, the constituent polymers maintained the bulk properties in 5–20 μm‐thick microlayers. The series model accurately described the gas transport properties of microlayered films. Comparison of blends and microlayers revealed that the high CO₂ selectivity of PEO was most effectively captured when the PEO phase was continuous, as in the microlayers or in the cocontinuous 50/50 (wt/wt) melt blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.