PVDF–PEO/ZSM-5 based composite microporous polymer electrolyte with novel pore configuration and ionic conductivity

A novel composite microporous polymer electrolyte based on poly(vinylidene fluoride), poly(ethylene oxide), and microporous molecular sieves ZSM-5 (denoted as PVDF–PEO/ZSM-5) was prepared by a simple phase inversion technique. PEO can obviously improve the pore configuration, such as pore size, porosity, and pore connectivity of PVDF-based microporous membranes, results in a high room temperature ionic conductivity. Microporous molecular sieves ZSM-5 can further improve the mechanical strength of PVDF–PEO blends and form special conducting pathway in PVDF–PEO matrix by absorb liquid electrolyte in its two-dimensional interconnect channels. The high room temperature ionic conductivity combined with good mechanical strength implies that PVDF–PEO/ZSM-5 based composite microporous polymer electrolyte can be used as candidate electrolyte and/or separator material for high-performance rechargeable lithium batteries.     

Electrical conductivity in TlI-TiO2 composite solid electrolyte

Composite materials of formula (1−x)TlI−xTiO₂, x=0-0.7, have been prepared and studied by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy and electrical conductivity. The materials were found to be binary phase systems with titania particles distributed between the grains of thallium iodide. The electrical conductivity got enhanced in the composition range x=0.1-0.5 and then decreased with further increase in the titania content. The behaviour is explained in terms of disordering phenomena at the interface regions and space-charge layers formed in the bulk grains of thallium iodide. Moreover, the increased content of titania in the system leads to the disappearance of order-disorder (β-α) phase transition in thallium iodide, which is usually observed in the pure compound. This behaviour was explained by the stabilizing effect of β-phase at high temperatures and at higher contents of titania. X-ray diffractograms do not show any indication to the presence of α-phase at ambient temperature, i.e. the phase could not be stabilized in the investigated system.     

A low cost composite quasi-solid electrolyte of LATP,TEGDME,and LiTFSI for rechargeable lithium batteries

The composite quasi solid state electrolytes(CQSE) is firstly synthesized with quasi solid state electrolytes(QSE) and lithium-ion-conducting material Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3(LATP), and the QSE consists of [LiG4][TFSI] with fumed silica nanoparticles. Compared with LATP, CQSE greatly improves the interface conductance of solid electrolytes. In addition,it has lower liquid volume relative to QSE. Although the liquid volume fraction of CQSE is droped to 60%, its conductivity can also reach 1.39 × 10~(-4)S/cm at 20℃. Linear sweep voltammetry(LSV) is conducted on each composite electrolyte.The results show the possibility that CQSE has superior electrochemical stability up to 5.0 V versus Li/Li+. TG curves also show that composite electrolytes have higher thermal stability. In addition, the performance of Li/QSE/Li Mn_2O_4 and Li/CQSE/Li Mn_2O_4 batteries is evaluated and shows good electrochemical characteristics at 60℃.     

A new hyperbranched star polyether electrolyte with high ionic conductivity

Hyperbranched poly(glycidol) containing hydroxyl groups was firstly synthesized via anionic polymerization and then reacted with 2-bromoisobutyl bromide to form macroinitiator HPG-Br. Finally, a hyperbranched star polymer (HPG-PPEGMA) was successfully prepared by atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether methacrylate using HPG-Br as macroinitiator. The structures and properties of the obtained polymers were characterized by ¹H NMR, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The ionic conductivity of the polymer electrolytes composed of HPG-PPEGMA and lithium bis(trifluoromethanesulfonimide) (LiTFSI) was investigated via electrochemical impedance spectroscopy. The results showed that the room temperature ionic conductivity of the prepared hyperbranched star polymer electrolytes had a higher ionic conductivity. When [EO]/[Li] was 20, the ionic conductivity of the hyperbranched star polymer electrolyte was up to 1?×?10^?4 Scm^?1 at 30 °C. The onset decomposition temperature of the hyperbranched star polyether could reach 374 °C, indicating that the hyperbranched star polymer had a good thermal stability. The XRD results showed that the structure of the hyperbranched star polymer was beneficial to improve the ionic conductivity due to possessing a low degree of crystallinity.     

Structural and ionic conductivity of PEO blend PEG solid polymer electrolyte

Structural and ionic conductivity of PEO blend PEG with KI solid polymer electrolyte system is presented. The polymer PEG showed miscible with the high molecular weight polymer PEO. The X-ray diffraction patterns of PEO/PEG with KI salt indicated the decrease in the degree of crystallinity with increasing concentration of the salt. The DSC measurements of PEO/PEG:KI polymer electrolyte system showed that the melting temperature is shifted towards the lower temperature with increase of the salt concentration. Optical micrographs demonstrated that the spherulites of different sizes are present along with dark regions between the spherulites for lower salt compositions. With increase of salt concentration more amorphous regions are observed. The significance of blend is the increase of one order in ionic conductivity when compared to without blend PEO electrolyte.     

Enhanced electrochemical,structural, optical,thermal stability and ionic conductivity of (PEO/PVP) polymer blend electrolyte for electrochemical applications

This paper reports the polyethylene oxide/polyvinylpyrrolidone (PEO/PVP) blend with cobalt chloride (CoCl₂) films prepared using spin coating method on blue star glass substrate. The XRD analysis shows the decrease in the crystallinity nature of the CoCl₂ with addition of the dopant. The FT-IR analysis reveals that interaction between cobalt ions with polymer blend confirms the complexation. The maximum ionic conductivity 0.65?×?10^?4 S cm^?1 was observed for PEO (45 %)/PVP (45 %)/CoCl₂ (10 %) at 30 °C. The optical energy band gaps decreases and Urbach energy were observed increases with increasing the dopant concentration. The DSC/TGA results showed that thermal stability of films enhanced with dopant concentration. Cyclic voltammogram (CV) study shows that the electrochemical strength improves with dopant concentration. These obtained results imply that polymer blend electrolytes are suitable candidature for various applications such as electronic and optical devices like electro-chromic display, fuel cells, gas sensors and solid state batteries.     

Pipe-sphere model for enhancement of ionic conductivity in composite solid electrolytes

It is well-known that the ionic conductivity of a superionic conductor when dispersed with an insulator shows a remarkable enhancement. In this work we suggest that the contribution coming from grain-boundaries and dislocations is primarily responsible for this phenomenon in a number of cases. We propose a simple theoretical model for such composites and with the aid of the Effective Medium Theory (EMT) under self-consistent scheme we estimate the effective conductivity as a function of insulator volume fraction and particle size for four composites, namely CaF₂-Al₂O₃, CuCl-Al₂O₃, Sr(NO₃)₂-Al₂O₃ and SrCl₂-Al₂O₃. This model is applicable to composites where enhancement is observed for a very low insulator volume fraction and other prevalent models are inadequate. The results exhibit a good qualitative fit to the experimental data and all characterisitic experimental observations.     

Effect of elaboration parameters on ionic conductivity for PECVD fuel cell electrolyte

Integration of fuel cells for nomad applications (like cell phone or notebook) is characterized by small dimensions and high performances of the component. To obtain theses properties, one of possibilities is to increase the active surface with patterned substrate. Then, the actual planar batteries must be replaced by 3D batteries. Most of deposition methods, used in the actual fuel cell process flow, are not compatible with the 3D deposition because they did not provide conformal coating. That is why we develop a PECVD electrolyte because this method is known to be compatible with 3D depositions. The PECVD electrolyte is based on a fluorocarboxylic acid, which is able to conduct protons. The obtained layer is a protonic conductor that can absorb water and stop hydrogen. Effects of elaboration parameters like pressure, power, or acid concentration on the ionic conductivity will be presented. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Polymer electrolyte plasticized with PEG-borate ester having high ionic conductivity and thermal stability

We have focused on the PEG-borate ester as a new type of plasticizer for solid polymer electrolyte composed of poly(ethyleneglycol) methacrylate (PEGMA) and lithium bis-trifluoromethanesulfonimide (LiTFSI). The PEG-borate ester shows good thermal stability and high flash point. Ionic conductivity of the polymer electrolyte increases with increasing amount of the PEG-borate ester and exhibits values greater than 10⁻⁴ S cm⁻¹ at 30 °C and 10⁻³ S cm⁻¹ at 60 °C. Furthermore, PEG-borate ester has three EO chains whose lengths are variable, and various ionic conductivities are expected to depend on EO chain length. As a result, polymer electrolyte containing the PEG-borate ester whose EO chain length is n=3 shows highest ionic conductivity. Furthermore, polymer electrolytes containing PEG-borate esters show excellent thermal and electrochemical stability. The electrolytes are thermally stable up to 300 °C and electrochemically up to 4.5 V vs. Li⁺/Li.     

Enhanced ionic conductivity at the interface between sapphire and solid lithium iodide

We have studied the enhanced ionic conductivity of thin films of LiI evaporated onto a planar sapphire surface carrying interdigital Au-electrodes. The interface conductivity parallel to the surface was measured in situ for increasing film thickness, up to 3,000 Å. The specific conductivity of LiI in the first 300 Å — adjacent to the sapphire — was found to exceed the bulk conductivity of LiI by nearly one order of magnitude. From our observations we conclude that the specific conductivity of LiI decreases exponentially with distance from the sapphire surface reaching the bulk LiI-value only at a distance of 3,000 Å. The conductivity of a 350 Å thick film varies with temperature (25°CT120°C) in accordance with an activation energy of 0.40±0.04 eV. This is in good agreement with the activation energy of bulk LiI in the extrinsic region.     

Enhanced conductivity in ionic conductor-insulator composites: numerical models in two and three dimensions

We describe a two-dimensional (2D) and a three-dimensional (3D) percolation model for ionic conductor-insulator composites such as copper(I) bromide-titanium dioxide (CuBr-TiO₂) or lithium iodide-alumina (LiI-Al₂O₃). These composites present an enhanced conductivity closely related to the insulator concentration. This effect is explained by the formation of highly conducting space charge regions near the phase boundaries which are represented by good conductor bonds. Our numerical model takes into account grain size and correlation effects. The dimension has a leading role for the conduction properties. In the 2D case, the good conductor bonds do not percolate, whatever the insulator concentration, and the maximum conductivity of the composite samples is of the same order as that of the ionic conductor grains. The behavior of the system is very different in the 3D case where, for a large domain of composition, the good conductors percolate through the regions between the conductor grains. For the CuBr-TiO₂ composites the conductivity versus composition curve is bell-shaped. Conversely, in the LiI-Al₂O₃ system, a linear relation between the conductivity and the insulator volume fraction is obtained in the experiments. Our model gives a plausible interpretation of the conductivity in both systems. Received 10 April 2001     

Structural and ionic conductivity studies on proton conducting polymer electrolyte based on polyvinyl alcohol

An attempt has been made to prepare a new proton conducting polymer electrolyte based on polyvinyl alcohol (PVA) doped with NH₄NO₃ by solution casting technique. The complex formation between polymer and dissociated salt has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared polymer electrolyte has been found by ac impedance spectroscopic analysis. The highest ionic conductivity has been found to be 7.5 × 10⁻³ Scm⁻¹ at ambient temperature for 20 mol% NH₄NO₃-doped PVA with low activation energy (~0.19 eV). The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship, which shows hopping of ions in the polymer matrix.     

Effects of plasticiser on the lithium ionic conductivity of polymer electrolyte PVC-LiCF3SO3

Solid polymer electrolyte films based on poly(vinyl chloride)-lithium triflate (PVC-LiCF₃SO₃) have been prepared by the solution-cast technique in various concentrations. The film with the highest conductivity was used to prepare plasticised polymer electrolyte films by using poly(ethlene glycol) (PEG) of different molecular weights, i.e., 200, 400 and 600 gmol⁻¹. These films were prepared to study the effects of addition of low molecular weights PEG on the lithium ionic conduction of the PVC based polymer electrolyte. The films were characterised by electrochemical impedance spectroscopy (EIS) and Fourier transform infrared-spectroscopy (FTIR). Results indicate that the molecular weight has an inverse effect on the conductivity and this has been accounted for by FTIR. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

About ionic conductivity/diffusion relationships in yttria doped zirconia

The values of the oxygen self-diffusion coefficients (measured using¹⁸O tracer) are compared to the ionic conductivity (measured by impedance spectroscopy) of 9.5 mol% yttria doped zirconia single crystals in the temperature range 240–800 °C in air. Electrical conductivity measurements in polycrystals, exhibiting a grain boundary contribution to the ionic conductivity, are furthermore discussed in the frame of a “brick/boundary model”. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Effect of hot pressing on the ionic conductivity of the PEO/LiCF3SO3 based electrolyte membranes

PEO/LiCF₃SO₃ (LiTFS) /Ethylene carbonate (EC) polymer electrolyte membranes were prepared with a solution casting method followed by a hot pressing process. The effect of the hot pressing process on the in-plane conductivity of the PEO electrolyte membranes was evaluated using a four-electrode AC impedance method. The composition, morphology, and microstructure of the composite polymer electrolyte were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The AC impedance measurement results indicate that the hot pressing process can increase the room temperature conductivity of the membranes 14 times to 1.7 × 10^− 3 S cm^− 1 depending upon the duration of the hot pressing process. The SEM, FTIR, XRD, and DSC results indicate that the hot pressing process could increase the amorphous part of the polymer electrolyte membrane or convert large spherulite crystals into nano-sized crystals.     

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.     

Entropy and ionic conductivity

It is known that the ionic conductivity can be obtained by using the diffusion constant and the Einstein relation. We derive it here by extracting it from the steady electric current which we calculate in three ways, using statistics analysis, an entropy method, and an entropy production approach.     

Enhanced ionic conductivity in La3+ and Sr2+ co-doped ceria: carbonate nanocomposite

Ionics - A series of ceria-based nanocomposites consisting of Ce0.85La0.125Sr0.025O1.9125 (LSCO) and binary carbonate mixture Li2CO3–Na2CO3 (LNCO) have been prepared as functional...     

Poly[lithium methacrylate-co-oligo(oxyethylene)methacrylate] as a solid electrolyte with high ionic conductivity

Poly[lithium methacrylate-co-oligo(oxyethylene)methacrylate] film was prepared as a polymeric solid electrolyte which showed lithium ionic conductivity of 2×10^?7(S/cm). This film contained no organic plasticizer nor low molecular weight lithium salts and shown to be a single-ion conductor in solid state. Li⁺ ionic conductivity was deeply influenced by the glass transition temperature and lithium methacrylate content of this film. A rechargeable battery composed of metallic lithium/this film/graphite showed better characteristics than any previously reported systems using polymeric solid electrolytes.     

Thermal conductivity of the pine-biocarbon-preform/copper composite

The thermal conductivity of composites of a new type prepared by infiltration under vacuum of melted copper into empty sap channels (aligned with the sample length) of high-porosity biocarbon preforms of white pine tree wood has been studied in the temperature range 5–300 K. The biocarbon preforms have been prepared by pyrolysis of tree wood in an argon flow at two carbonization temperatures of 1000 and 2400°C. From the experimental values of the composite thermal conductivities, the fraction due to the thermal conductivity of the embedded copper is isolated and found to be substantially lower than that of the original copper used in preparation of the composites. The decrease in the thermal conductivity of copper in the composite is assigned to defects in its structure, namely, breaks in the copper filling the sap channels, as well as the radial ones, also filled by copper. A possibility of decreasing the thermal conductivity of copper in a composite due to its doping by the impurities present in the carbon preform is discussed.