Transport studies of NH4NO3 doped methyl cellulose electrolyte

This work reports on the transport properties of NH₄NO₃ doped methyl cellulose (MC) polymer electrolyte. The polymer electrolyte films were prepared by the technique of solvent casting. The highest room temperature conductivity of MC doped with 25 wt.% NH₄NO₃ is 2.10 ± 0.37 × 10^?6 S cm^?1. Conductivity–temperature relationship obeys the Vogel–Tamman–Fulcher (VTF) rule from which the glass transition temperature, T_g was evaluated. The mobility, μ and number density of charge carrier, n were calculated using the Rice and Roth model.     

Impedance spectroscopy properties of polypyrrole doped with boric acid

The electrical conductivity and dielectric properties of polypyrrole doped with boric acid have been investigated. The direct current conductivity (dc) of the polymer increases with increasing temperature. The alternating current (ac) conductivity of the polymer obeys the power law, i.e., σ_ac(ω) = Aω^s. The alternating conductivity of polypyrrole doped with boric acid is controlled by the correlated barrier hopping model. The activation energy for alternating current mechanism decreases with increasing frequency which confirms the hopping conduction to the dominant mechanism as compared with the dc activation energy. The density of localized states N(E_F) for polypyrrole doped with boric acid was in the range of 2.5–9.2 × 10²² cm^?3 for various temperatures. The dielectric relaxation mechanism was explained on the basis of complex dielectric modulus. The imaginary modulus plot at different temperatures shows a dielectric mechanism with non-Debye relaxation. Boric acid can be a good candidate for controlling the electrical conductivity of the conducting polymer.     

High thermoelectric performance of poly(2,5-dimethoxyphenylenevinylene) and its derivatives

Poly(2,5-dimethoxyphenylenevinylene) (PMeOPV) and a series of copolymers consisting of both 2,5-dimethoxy-substituted phenylenevinylene units and unsubstituted units (P(MeOPV-co-PV)) were evaluated from the viewpoint of their thermoelectric properties. Their conjugated polymer films were prepared by pyrolysis of stretched or unstretched films of sulfonium salt precursor polymers, and subsequently doped with iodine vapor to provide electrical conductivity. The power factors P (=S²σ), indicating thermoelectric performance, were calculated with the measured electrical conductivity σ and Seebeck coefficient S of the doped films. PMeOPV showed a higher power factor of 7.1 μW m⁻¹ K⁻² at 313 K than that of a camphorsulfonic acid-doped polyaniline as reference. P(MeOPV-co-PV) precursor polymers with less than 20 mol% of MeOPV unit content in the monomer feed were stretchable, therefore providing stretched P(MeOPV-co-PV) films with low MeOPV unit content. The stretching treatment for P(MeOPV-co-PV) enhanced its electrical conductivity, but kept the Seebeck coefficient at nearly the same level as that of unstretched polymers. Consequently a 4.4-fold stretched copolymer exhibited an electrical conductivity of 183.5 S/cm and a Seebeck coefficient of 43.5 μV/K at 313 K, and thus, its power factor at 313 K was over 30 μW m⁻¹ K⁻². To the best of our knowledge, this is the highest thermoelectric performance ever reported among conducting polymers.     

Optical investigation of intra and interchain charge dynamics in conducting polymers

Reflectance measurements on tensile-drawn films of polypyrrole (PPy) doped with PF₆ are analyzed in terms of intra and interchain contributions to the optical conductivity σ(ω). The intrachain σ(ω) is typical of a disordered Drude metal with σ(ω→0)≈2×10³ S/cm, while the interchain σ(ω) is dominated by spectral features of strongly localized conductors, implying the interchain charge dynamics is incoherent.     

Doped polypyrrole for MAPLE deposition: Synthesis and characterization

The contribution deals with synthesis and characterization of conductive polypyrrole (PPY), which should be suitable for depositions of thin layers by Matrix Assisted Pulsed Laser Evaporation (MAPLE) method. The samples of doped PPY containing various organic dopants – (i) p-toluenesulfonic acid, (ii) dodecyl-benzenesulfonic acid, (iii) dioctyl-sulfosuccinic acid and (iv) camphorsulfonic acid – were synthesized by polymerization of pyrrole in acidic or neutral solution. Solubility of synthesized PPY and settlement time of PPY particles in water and dimethylsulfoxide – parameters critical for MAPLE method – were investigated. The composition of prepared PPY was verified by FTIR spectroscopy. Conductivity of the polymer in solid state was determined to be in range from σ = 2.6 × 10^?6 S cm^?1 to σ = 6.0 × 10^?2 S cm^?1. The optimal material for MAPLE deposition is PPY containing organic dopants (ii)–(iv), dissolved in DMSO matrix (solubility from 4.1% to 6.5% by weight and settlement time 140–240 h).     

Ionic liquid doped poly(N-methyl 4-vinylpyridine iodide) solid polymer electrolyte for dye-sensitized solar cell

Ion conducting polymer electrolyte, poly(N-methyl 4-vinylpyridine iodide) (PVPI) is synthesized for dye-sensitized solar cell (DSSC) application. A new solid polymer electrolyte composite containing low viscosity ionic liquid (IL) 1-ethyl 3-methylimidazolium dicyanamide (EMImDCN) doped PVPI is developed and its structural, electrical and photoelectrochemical studies are presented in detail. Fourier transform infrared (FTIR) spectroscopy, proton NMR and atomic force microscopy (AFM) affirms the modified polymer and its composite nature with porous surface morphology. The developed solid polymer electrolyte shows enhancement in ionic conductivity (σ) due to IL doping. The maximum σ value of 9.12 × 10^?6 S cm^?1 was obtained at 40 wt% IL concentration. The redox behavior of the electrolyte has been verified by the cyclic voltammetry studies. For device application, we have fabricated a DSSC using this solid polymer–IL electrolyte system which shows energy conversion efficiency of the solid-state cell as 0.65% under irradiation of simulated sunlight (AM 1.5, 100 mW cm^?2).     

High molecular weight soluble polypyrrole

High molecular weight, soluble, doped polypyrrole containing no substituent on the pyrrole ring has been synthesized by the incorporation of the novel, versatile di(2-ethylhexyl) sulfosuccinate dopant anion which renders the polymer soluble in polar and also weakly polar or non-polar solvents. The M_w values corresponding to at least 303 pyrrole rings/polymer chain are observed in material which has at least 9 wt./vol.% solubility in NMP and significant solubility in solvents such as DMSO, DMF and m-cresol, etc. Free standing films exhibited conductivities ranging from ∼3 to 10⁻³ S/cm depending on the solvent from which they were cast. Films cast from NMP could be stretched to 2.5 times their original length to give a conductivity, σ, of ∼60 S/cm. The degree of crystallinity of films differed depending on the solvent from which they were cast. The TGA and DSC studies showed that the decomposition temperature was limited by the dopant anion.     

Electrochemical polymerization of 9-cyanophenanthrene and characterization of its polymer

A novel conducting polymer poly(9-cyanophenanthrene) (P9CP) was synthesized electrochemically by direct anodic oxidation of 9-cyanophenanthrene (9CP) in boron trifluoride diethyl etherate (BFEE). The oxidation onset potential of 9CP in the medium was measured to be 1.6 V vs. a saturated calomel electrode (SCE). P9CP films obtained from BFEE showed good electrochemical behavior and good thermal stability with electrical conductivity of 0.13 S cm^?1 in the doped state. The polymer of P9CP may be an attractive candidate material for organic light-emitting material with blue-green-light-emitting upon irradiation with 365 nm UV light. Moreover, the P9CP films on the ITO electrode showed good electrochromic property from dark green to dark yellow, between the doped and dedoped state. FTIR and the quantum chemistry calculation indicated that the 9CP was grown via the coupling of the monomer mainly at the C₃, and C₁₂ positions.     

Structure–conductivity relationships in chemical polypyrroles of low,medium and high conductivity

Chemically synthesized polypyrroles of low (σ < 75 S/cm), medium (75 < σ < 200 S/cm) and high (σ > 200 S/cm) electrical conductivity (σ) with the same dopant and degree of doping have been investigated by means of Wide Angle X-ray Scattering (WAXS), ¹³C Cross Polarized Magic Angle Spinning Nuclear Magnetic Resonance (¹³C CP/MAS NMR) spectroscopy and Fourier Transform Infrared (FTIR) Spectroscopy to establish structure–conductivity relationships useful for industrial applications. A similar amorphous structure was found by WAXS even for the higher conducting PPy (σ = 288 S/cm). WAXS spectra for polypyrroles of medium and high conductivity showed a weak peak at 2θ = 10–11° due to improved order of the counterions in these materials. The effect of the counterion size in the asymmetry of the PPy main WAXS peak was elucidated by performing ion exchange of the Cl⁻ dopant with counterions of larger size such as BF₄⁻ and ClO₄⁻. From ¹³C CP/MAS NMR measurements predominantly α–α′ bonding was found in these materials. The main ¹³C CP/MAS NMR resonance peak of PPy located at 126–128 ppm was broadened upon increasing conductivity. Interestingly, a linear relationship was observed between the half-width at half-height (HWHH) of the ¹³C CP/MAS NMR peak and conductivity where a doubling of the polypyrrole conductivity leads to an increase of HWHH by 6–7 ppm. FTIR data of these materials were analysed in the framework of the Baughman–Shacklette theory describing the dependence of conductivity on conjugation length. By comparison of model predictions and experimental results, the PPy samples were found to be in the regime of long conjugation lengths, L ≫ K₂/k_BT, where K₂ is a parameter related to the energy change on going from j − 1 to j charges on a conjugated segment of conjugation length L, k_B the Boltzman constant and T is the absolute temperature.     

Oxidative electropolymerization of pyrrole from neat monomer solution

Oxidative electrochemical polymerization of pyrrole at gold, indium doped tin oxide on glass, and stainless steel type 304 was accomplished from neat monomer solution containing only supporting electrolyte (0.05–0.3 M n-tetrabutyl ammonium perchlorate, n-tetrabutyl ammonium hexafluorophosphate, or n-tetrabutyl ammonium tetrafluoroborate) by multiple scan cyclic voltammetry. The results presented demonstrate that thick (>1–14 μm), stable, highly conductive (up to 0.6 S/cm) polypyrrole films can be readily prepared on a wide range of electrode substrates using this simple electrochemical method.     

Characterization of conducting polymer coated synthetic fabrics for heat generation

Heat generation in fabrics coated with the conductive polymer polypyrrole was investigated. The PET fabrics were coated by chemical synthesis using four different oxidizing agent–dopant combinations. The samples from the four different dopant systems all show an increase in temperature when a fixed voltage is applied to the fabric. The antraquinone-2-sulfonic acid (AQSA) sodium salt doped polypyrrole coating was the most effective in heat generation whereas the sodium perchlorate dopant system was the least effective. The power density per unit area achieved in polypyrrole coated polyester–Lycra® fabric with 0.027 mol/l of AQSA acting as dopant was 430 W/m². The power density per unit area achieved for the sodium perchlorate system, using the same synthesis conditions, was 55 W/m².     

Electrochemical synthesis of novel conducting polymer composite: Polypyrrole–pentacyanonitrosylferrate

With a view to develop conducting polymer film of high electroactivity, pentacyanonitrosylferrate (PCNFe) doped polypyrrole (PPY) composite films are prepared using cyclic voltammetry deposition method. The PPY–PCNFe composite is characterized by FTIR, TEM and TGA analysis. The electroactivity of PPY–PCNFe composite film is studied in 3 mM KCl (common electrolyte) solution. Two redox pairs at E_1/2 = ?0.59 V and 0.02 V due to redox behavior of polymer and dopant anions respectively are observed. The electroactivity study reveals the existence of two types of PCNFe dopant anions in the polymeric film: one form is loosely held and prone to easy removal from the polymer matrix whereas the other form is strongly bound to polymer backbone and prone to electrochemical redox reaction by movements of electrons. The high electroactivity of the film is attributed to the movements of ionic species into and out of the polymeric film as well as movements of electron.     

Preparation and electrical–magnetic properties of polyaniline doped with ionic ferrocenesulfonic acid

Conducting polyaniline with electrical conductivity of 2.34 × 10⁻¹ S cm⁻¹ was obtained using ferrocenesulfonic acid as dopant. After the ferrocenesulfonic acid was oxidized with FeCl₃, though the electrical conductivity of the doped polyaniline decreased by 1–2 orders of magnitude, the magnetic susceptibility (χ) increased with the increase of the oxidation degree of ferrocenesulfonic acid. EPR spectra showed not only a signal with a g value of around 2, but also a so-called half-field signal with a g value of about 4 even at room temperature. Coexistence of ferromagnetic intrachain interactions and antiferromagnetic interchain interactions in the materials has been suggested.     

Electrical properties,sintering and thermal expansion behavior of composite ceramic interconnecting materials,La0.7Ca0.3CrO3−δ/Y0.2Ce0.8O1.9 for SOFCs

This paper presents a high-performance interconnect ceramic for solid oxide fuel cells (SOFCs), based on a modification of La_0.7Ca_0.3CrO_3−δ (LCC). It was found that addition of a small amount of YDC (Y_0.2Ce_0.8O_1.9) into LCC dramatically increased the electrical conductivity. For the best system, LCC + 3 wt.% YDC, the electrical conductivity reached 104.8 S cm⁻¹ at 800 °C in air. The electrical conductivity of the specimen with 2 wt.% YDC in H₂ at 800 °C was 5.9 S cm⁻¹. With the increase of YDC content, the relative density increased, reaching 97.6% when the YDC content was 10 wt.%. The average coefficient of thermal expansion (CTE) at 30–1000 °C in air increased with YDC content, ranging from 11.12 × 10⁻⁶ K⁻¹ to 15.34 × 10⁻⁶ K⁻¹. The oxygen permeation measurement illustrated a negligible oxygen ionic conduction, indicating that it is still an electronically conducting ceramic. Therefore, it is a very promising interconnecting ceramic for SOFCs.     

Synthesis,crystal structure and electrical conductivity of [bmim][Ni(dmit)2]3 (bmim = 1-butyl-3-methylimidazolium,dmit = 1,3-dithiol-2-thione-4,5-dithiolate)

A new complex [bmim][Ni(dmit)₂]₃ has been prepared, and its crystal structure and electrical conductivity where determined and measured. Crystallographic parameters for C₂₆H₁₅N₂S₃₀Ni₃: triclinic system; space group: P-1; a=12.760(3), b=19.441(4), c=11.670(2) Å; α=102.00(3), β=117.10(3), γ=95.06(3)°; Z=2, R=0.0579 (I>2σ(I)). The conductivity of this salt at room temperature is 1.7×10⁻² S cm⁻¹ and it shows semiconduction in the temperature range of 110–290 K.     

Organic conductor: Influence of preparation temperature

The conducting polypyrrole–polyethylene glycol (PPy–PEG) composite films were produced at various polymerization temperature ranging from 5 °C to 60 °C using 1 × 10^?3 M PEG, 0.20 M pyrrole and 0.10 M p-toluene sulfonate at 1.20 V (vs. SCE). The polymerization temperature of 5 °C appeared as the optimum preparation temperature showing the highest electrical conductivity of 70 S/cm and the thermal diffusivity of 8.76 × 10^?7 m² s^?1. The electrical conductivity and thermal diffusivity exhibited a decreasing trend with the increase in polymerization temperature in the pyrrole solution used to prepare the composite films. The XRD results reveal that low temperature (5 °C) typically results in more crystalline films, which are denser, stronger and have higher conductivity. The optical microscopy of PPy–PEG shows the globular surface morphology. The surface of the of the solution side of PPy–PEG film prepared at low temperatures showed a globular morphology.     

High-temperature thermoelectric properties of Sr2RuYO6 and Sr2RuErO6 double perovskites influenced by structure and microstructure

The high-temperature thermoelectric properties of Sr₂RuYO₆ and Sr₂RuErO₆ double perovskites were evaluated and reported for the first time. These compounds show high Seebeck coefficients not only at room temperature, but also at high temperature (for Sr₂RuYO₆, S_RT ≈ ?475 μV K^?1 and S_1200K ≈ ?250 μV K^?1; Sr₂RuErO₆, S_RT ≈ ?400 μV K^?1 and S_1200K ≈ ?250 μV K^?1). The n-type semiconducting behaviour dominates the resistivity values. Both compounds crystallize in a monoclinic unit cell (space group P2₁/n). The lattice parameters are a = 5.7761(2), b = 5.7804(1), c = 8.1689(1), α = γ = 90° and β = 90.2087(8)° for the Sr₂RuYO₆, and a = 5.7760(1), b = 5.7722(0), c = 8.1544(4), α = γ = 90° and β = 90.2099(7)° for Sr₂RuErO₆. The unit cell can be described approximately as √2a_p × √2a_p × 2a_p, where a_p is the unit cell parameter of the ideal cubic perovskite structure. High-resolution transmission electron microscopy shows an interesting three-dimensional micro-twin-domain texture where the c axis is placed in the three space directions. Structural transitions at high temperatures (T_t(Sr₂RuYO₆) ≈920 K and T_t(Sr₂RuErO₆) ≈890 K) are observed by specific heat measurement in both compounds, which are found to have a strong influence on the Seebeck coefficient and electrical conductivity.     

Electrical behavior of conducting polymer based ‘polymeric–inorganic’ nanocomposite: Polyaniline and polypyrrole zirconium titanium phosphate

Composites are 21st century material used to meet the demand of improved materials and possess a combination of several desirable properties. Present study focussed on the conducting behavior of ‘polymeric–inorganic’ nanocomposite of conducting polymer polyaniline and polypyrrole. ‘Polymeric–inorganic’ nanocomposite cation-exchangers, i.e., polyaniline zirconium titanium phosphate (PANI-ZTP) and polypyrrole zirconium titanium phosphate (PPy-ZTP), were synthesized via sol–gel mixing of electrical conducting polymers into the matrices of inorganic precipitate of zirconium titanium phosphate (ZTP) having excellent ion exchange properties. The proposed nanocomposite possessed DC electrical conductivity in the semi-conducting range, i.e., 10^?5–10^?3 S cm^?1. The stability in terms of DC electrical conductivity retention was also studied in an oxidative environment by two slightly different techniques viz. isothermal and cyclic techniques. The DC electrical conductivity of composite material was found stable upto 110 °C under ambient conditions.     

Synthesis and characterization of aniline copolymers containing carboxylic groups and their application as sensitizer and hole conductor in solar cells

Copolymers of m-aminobenzoic acid and o-anisidine doped with p-toluenesulphonic acid in different proportions were successfully synthesized by oxidative polymerization. The copolymers were characterized by FT-IR, UV–vis, ¹H NMR and EPR spectroscopies, cyclic voltammetry, conductivity and SEM. The copolymer with equivalent amounts of the monomers o-anisidine and m-aminobenzoic acid presented the highest conductivity, The EPR analyses and SEM images show that this copolymer provides more homogeneous films with particle size distribution of approximately 1–2 μm. The copolymer with a high fraction of o-anisidine gives rises to films with larger particle sizes and a more defined electrochemical process. The m-aminobenzoic acid monomer was intentionally chosen in order to promote a better electronic coupling between the conducting copolymer and the TiO₂ surface. The copolymers were tested as both sensitizers and hole conducting materials in dye-sensitized solar cells. The device assembled using the copolymer with the highest proportion of m-aminobenzoic acid units as sensitizer produced the highest photocurrent (I_sc = 0.254 mA cm^?2) and photovoltage (V_oc = 0.252 V) at 100 mW cm^?2. The energy diagram shows that although the electronic injection from the conducting polymer excited state is an allowed process the regeneration of the positive charges created after the electron transfer process is forbidden, thus explaining the low efficiency of solar energy conversion. When this copolymer was applied as a hole conducting material, an improvement in the V_oc to 0.4 V, was observed, indicating that this material is more suitable for charge transport when applied in this type of solar cells.     

Influence of counter-ion concentration on properties of electrochemically generated poly-N-methylpyrrole (PNMPy/ClO4)

This is a study of the relationship observed between the synthesis conditions and polymer properties in electrochemically generated poly-N-methylpyrrole (PNMPy). The best values are given for overpotentials of synthesis and perchlorate concentration that provide a polymer with improved conductivity and electrochemical properties. In this way a film was obtained with a conductivity of 1.3 S m⁻¹. The morphology, electronic spectrum and stability of the film were determined. An equation was determined relating film thickness and polymerization charge density.