Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10⁻⁴ to 10⁻³ S cm⁻¹ at room temperature. Gelation was found to cause little change in the ⁷Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids.

PEDOT-coated counter electrodes for dye-sensitized solar cells

Poly(3,4-ethylenedioxythiophene) (PEDOT)-coated counter electrodes for dye-sensitized solar cells have been prepared at ambient temperature and without the use of iron-based oxidants, using an ionic liquid for the synthesis of the PEDOT. These electrodes show comparable electrocatalytic performance with conventional Pt-coated counter electrodes (solar cell efficiencies >7.5%).

Conducting polymers with fibrillar morphology synthesized in a biphasic ionic liquid/water system

The synthesis of poly(pyrrole), poly(terthiophene), and poly(3,4-ethylenedioxythiophene) with unusual fibrillar morphologies has been achieved by chemical polymerization in a biphasic ionic liquid/water system. Use of aqueous gold chloride as the oxidant, with the monomers dissolved in a hydrophobic ionic liquid, allows the polymerization to occur at the ionic liquid/water interface. The resultant conducting polymer fibrils are, on average, 50−100 nm wide and can be thousands of nanometers long. The polymers produced in this ionic liquid system are compared to those synthesized in a biphasic chloroform/water system.

Investigation of the electropolymerisation of EDOT in ionic liquids

Poly(3,4-ethylenedioxythiophene) (PEDOT) has been successfully synthesised using ionic liquids as both the growth medium and the electrolyte. Both imidazolium and pyrrolidinium-based TFSA ionic liquids were used to assess the influence of the nature of the medium on the morphology and electrochemical activity of the resulting materials.

Control of magnesium interfacial reactions in aqueous electrolytes towards a biocompatible battery

A stable magnesium battery has been developed based on a magnesium anode, a poly(dioxyethane thiophene) (PEDOT) cathode and a near-saturated aqueous solution of LiCl, MgCl₂, or mixture of these salts at pH of 11. This combination leads to a low water activity in the electrolyte, which thus suppresses the hydrogen evolution reaction on Mg, as well as producing a stable oxy-hydroxide film which protects the metal surface from freely corroding. The conducting polymer cathode is reduced somewhat during the discharge process, however, appears to be readily re-oxidised (as determined from the resistance) by the oxygen present in the cell. The cell is therefore primarily a Mg/O₂ battery, however, the PEDOT appears to enhance the performance, in particular the discharge voltage.

High rates of oxygen reduction over a vapor phase-polymerized PEDOT electrode

The air electrode, which reduces oxygen (O₂), is a critical component in energy generation and storage applications such as fuel cells and metal/air batteries. The highest current densities are achieved with platinum (Pt), but in addition to its cost and scarcity, Pt particles in composite electrodes tend to be inactivated by contact with carbon monoxide (CO) or by agglomeration. We describe an air electrode based on a porous material coated with poly(3,4-ethylenedioxythiophene) (PEDOT), which acts as an O₂ reduction catalyst. Continuous operation for 1500 hours was demonstrated without material degradation or deterioration in performance. O₂ conversion rates were comparable with those of Pt-catalyzed electrodes of the same geometry, and the electrode was not sensitive to CO. Operation was demonstrated as an air electrode and as a dissolved O₂ electrode in aqueous solution.

Synthesis and characterization of soluble conducting polymers

Although conducting polymers have various potential applications, lack of solubility is an impediment in their direct application to material surfaces. Synthesis of alkyl pyrrole monomers and subsequent polymerization into soluble conducting polymers are aimed as alternatives to conventional methods of application of conducting polymers on substrates. Alkyl chains are attached to a pyrrole ring to produce solubility in the resulting conducting polypyrroles, which allow direct application of conductive polymer emulsions to any desired surface. Friedel-Crafts acylation of the tosyl-protected pyrrole provides high yields of the 3-acylated product. The conductivity values of poly-3- and 3, 4-substituted pyrroles are generally less than the unmodified polypyrrole. Increasingly bulkier groups attached to the pyrrole means lower conductivity of the resultant polymer. As the carbon chain length attached to the 3-position of pyrrole increases, the solubility also increases. However, the magnitude of change in conductivity of films and pellets of soluble conducting polypyrroles over the alkyl range is not significant.

Methods of coating textiles with soluble conducting polymers

Soluble conducting alkyl polypyrrole polymers have been applied by either chemical polymerization of the 3-alkyl monomers or direct application of polymer emulsion to the surface. Solution, vapor and spray polymerization methods of coating poly(3-alkylpyrroles) to the surface of woven wool fabrics are explored. Conductive textile samples have also been prepared by applying emulsions of soluble prepolymerized 3-alkylpyrrole to the fabric surface. Direct applications of a conductive paint to the textile surface eliminate the exposure of the substrate to damaging oxidizing agents which allow the coating of more sensitive and delicate substrates. All textiles produced are tested for abrasion resistance and conductivity. For alkyl polypyrrole coated fabrics, the optimum carbon chain lengths are between n=10 and n=14, which result in optimum values of conductivity and solubility. The darkness of the tone is inversely related to the surface resistivity of the resulting conductive fabric. Therefore, deep black coatings have low resistivity whereas light gray coatings on a white fabric surface have higher surface resistivity. Longer alkyl chains result in higher surface resistivity in fabrics. The conductive coating of poly(3-decanylpyrrole) on the textile surface has a better abrasion resistance compared to that of an unsubstituted polypyrrole coating.

Mobile agent tracking with single frequency continuous wave radar : a linear robust filtering based approach

3-alkylpyrrole to the fabric surface. Direct applications of a conductive paint to the textile surface eliminate the exposure of the substrate to damaging oxidizing agents which allow the coating of more sensitive and delicate substrates. All textiles produced are tested for abrasion resistance and conductivity. For alkyl polypyrrole coated fabrics, the optimum carbon chain lengths are between n=10 and n=14, which result in optimum values of conductivity and solubility. The darkness of the tone is inversely related to the surface resistivity of the resulting conductive fabric. Therefore, deep black coatings have low resistivity whereas light gray coatings on a white fabric surface have higher surface resistivity. Longer alkyl chains result in higher surface resistivity in fabrics. The conductive coating of poly(3-decanylpyrrole) on the textile surface has a better abrasion resistance compared to that of an unsubstituted polypyrrole coating.

A new route to nanostructured thermosets with block ionomer complexes

We report a novel approach to prepare nanostructured thermosets using block ionomer complexes. Neither block copolymer polystyrene-block-poly(ethylene-ran- butylene)-block-polystyrene (SEBS) nor block ionomer sulfonated SEBS (SSEBS) is miscible with diglycidyl ether of bisphenol A (DGEBA) type epoxy resin. It is thus surprising that the block ionomer complex of SSEBS with a tertiary amine-terminated poly(3-caprolactone) (PCL), denoted as SSEBS-c-PCL, can be used to prepare nanostructured epoxy thermosets. The block ionomer complex SSEBS-c-PCL is synthesized via neutralization of SSEBS with 3-dimethylamino- propylamine-terminated PCL. Sulfonation of SEBS yields the block ionomer SSEBS which is immiscible with epoxy. But the block ionomer complex SSEBS-c-PCL can be easily mixed with DGEBA. When the curing agent 4,4'-methylenedianiline (MDA) is added and the epoxy cures, the system retains the nanostructure. In cured epoxy thermosets containing up to 30 wt% SSEBS-c-PCL, the exclusion of the poly(ethylene-ran-butylene) (EB) phase forms spherical micro-domains surrounded by separated sulfonated polystyrene phase while the PCL side-chains of SSEBS-c-PCL are dissolved in the cured epoxy matrix. The spherical micro-domains are highly aggregated in the epoxy thermosets containing 40 and 50 wt% SSEBS-c-PCL. The existence of epoxy-miscible PCL side-chains in the block ionomer complex SSEBS-c-PCL avoids macro-phase separation. Hence, the block ionomer complex can act as an efficient modifier to achieve nanostructured epoxy thermosets.

Influence of ionic liquids on the electrical conductivity and morphology of PEDOT:PSS films

Small-molecule nonvolatile additives based on ionic liquids (IL) as electrical conductivity enhancer in Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) was studied. Ionic liquids were investigated in the synthesis of self-assembled, highly organized hybrid nanostructures due to their ability as supramolecular solvents. Different percentage of five ionic liquids, such as 1-butyl-3-methylimidazolium tetrafluoroborate (bmim) F 4 and 1-butyl-3-methylimidazolium bromide (bmim)Br were added to a PEDOT:PSScommercial dispersion. Films of pure PEDOT:PSS showed an average conductivity of 14 S cm-1, which corresponded to the value range given by the supplier. AFM images showed that IL induced the formation of a three-dimensional conducting network with smaller PEDOT domains. The ionic character of the films was significantly increased because of the presence of ionic liquids, which can be used effectively in optoelectronic devices.

Novel dithiolene complexes incorporating conjugated electroactive ligands

A series of new metal (M) dithiolene complexes bearing terthiophene (3, 12, M = Ni; 4, M = Pd; 5, 6, M = Au) and 2,5-bis(para-methoxyphenyl)thiophene units (14, M = Ni; 15, 16, M = Au; 17, M = Pd) have been synthesised in 38–99% yield. The electrochemical properties of the materials have been characterised by cyclic voltammetry and UV-vis spectroelectrochemistry. The nickel complexes possess low oxidation potentials (−0.12 to −0.25 V vs Ag/AgCl) due to the electron-rich dithiolene centres and all complexes display ligand-based redox activity. The terthiophene derivatives have been polymerised by electrochemical oxidation to give stable films with, in the case of poly(3), broad absorption characteristics. Charge transfer materials have been isolated from 14 and 16 with conductivities in the range 9 × 10⁻⁶ to 7 × 10⁻⁸ S cm⁻¹.

Nanofibrous p-n junction and its rectifying characteristics

Randomly oriented tin oxide (SnO2) nanofibers and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)/polyvinylpyrrolidone (PEDOT:PSS/PVP) nanofibers were prepared by a two-step electrospinning technique to form a layered fibrous mat. The current-voltagemeasurement revealed that the fibrousmat had an obvious diode-rectifying characteristic. The thickness of the nanofiber layers was found to have a considerable influence on the device resistance and rectifying performance. Such an interesting rectifying property was attributed to the formation of a ??-?? junction between the fibrous SnO2 and PEDOT:PSS/PVP layers. This is the first report that a rectifying junction can be formed between two layers of electrospun nanofiber mats, and the resulting nanofibrous diode rectifier may find applications in sensors, energy harvest, and electronic textiles.

Exploiting high quality PEDOT:PSS–SWNT composite formulations for wet-spinning multifunctional fibers

In order to exploit the inherent properties of carbon nanotubes (CNT) in any polymer composite, systematic control of carbon nanotube loading and protocols that mitigate against CNT bundling are required. If such composites are to be rendered in fiber form via wet-spinning, then CNT bundling during the coagulation process must also be avoided. Here we have achieved this by utilizing highly exfoliated single walled carbon nanotubes (SWNT) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonicacid) (PEDOT:PSS) to obtain wet-spinnable composite formulations at various nanotube volume fractions (Vf). The addition of only 0.02 Vf of aggregate-free and individually dispersed SWNT resulted in a significant enhancement of modulus, tensile strength, electrical conductivity and two cell electrode specific capacitance of PEDOT:PSS–SWNT composite fibers to 5.2 GPa, 200 MPa, 450 S cm−1 and 59 F g−1 by the rate of dY/dVf = 89 GPa, dσ/dVf = 3.2 GPa, dS/dVf = 13 300 S cm−1 and 6 folds, respectively.