Capacitance properties of poly(3,4-ethylenedioxythiophene)/carbon nanotubes composites

The electrochemical properties of composites prepared from an electrically conducting polymer poly(3,4-ethylenedioxythiophene), i.e. PEDOT and multiwalled carbon nanotubes (CNTs) have been investigated for supercapacitor application. The novel composite material was prepared by chemical or electrochemical polymerization of EDOT directly on the nanotubes or from a homogenous mixture of PEDOT and CNTs. Acetylene black (AB) has been also used as a composite component in order to evaluate whether nanotubes are giving improved properties or not. Electrodes prepared from such composites were used in supercapacitors operating in acidic (1 M H₂SO₄), alkaline (6M KOH) and organic (1 M TEABF₄ in AN) electrolytic solutions. The capacitance values were estimated by galvanostatic, voltammetry and impedance spectroscopy techniques with two- or three-electrode cell configuration. Due to the open mesoporous network of nanotubes, the easily accessible electrode/electrolyte interface allows quick charge propagation in the composite material and an efficient reversible storage of energy in PEDOT during subsequent charging/discharging cycles. The composites with AB supply quite good capacitance results, however, nanotubes as electrode component gave definitively a more homogenous dispersion of PEDOT that should give a better charge propagation. The values of capacitance for PEDOT/carbon composites ranged from 60 to 160 F/g and such material has a good cycling performance with a high stability in all the electrolytes. Organic medium is especially interesting because of higher energy stored. Another quite important advantage of this composite is its significant volumetric energy because of the high density of PEDOT.     

Preparation and characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) using partially sulfonated poly(styrene-butadiene-styrene) triblock copolymer as a polyelectrolyte

An aqueous dispersion of poly(3,4-ethylenedioxythiophene) (PEDOT) was prepared using a partially sulfonated poly(styrene-b-butadiene-b-styrene) (s-SBS) as a polyanion. For the preparation of s-SBS, poly(styrene-b-butadiene-b-styrene) was sulfonated to four different levels ranging from 44.1 to 64.8 mol%. These sulfonated polymers were characterized with IR spectroscopy and ¹H NMR analysis to confirm sulfonation reaction. The preparation of the PEDOT complex was carried out through the chemical polymerization method in which the EDOT monomer starts to polymerize in the presence of s-SBS, resulting in an aqueous dispersion of PEDOT/s-SBS complex. The DC conductivities of PEDOT/s-SBS complexes were found to increase from 0.0003 to 0.05 s/cm as the sulfonation level of the corresponding s-SBS increases, which is consistent with the data recorded by UV–vis spectrophotometer. From the XPS experiments, it was concluded that the concentration of PEDOT-rich phase in the PEDOT/s-SBS increases as the sulfonation level of s-SBS increase, thus facilitating the charge transport along the doped PEDOT chains.     

Poly(3,4-ethylene dioxythiophene): Poly(styrene sulfonate)的共振拉曼光谱研究

通过拉曼光谱方法分别对PEDOT:PSS掺杂和去掺杂状态进行了详细分析. 实验结果表明, 去掺杂的PEDOT:PSS由于其在激发波长附近的吸收增强而引起了共振效应, 拉曼信号得到大幅度增强, 可见, 以633 nm(He-Ne)激光为激发波长的拉曼光谱是研究PEDOT:PSS掺杂状态的有效方法. 此外, 显微拉曼光谱也是分析聚合物发光二极管器件内各层材料的有效手段.     

Effect of polymer relaxation on dielectric spectroscopic study of polymer–ferroelectric liquid crystal composites

Polymethylmethacrylate (PMMA) and ferroelectric liquid crystal (P–FLC) composite films (~ 4 μm) with varying proportions of ferroelectric liquid crystal have been prepared and the dielectric response of the composite films as a function of wide frequency (100 Hz–10 MHz) and temperature (127–40 °C) have been analyzed. The dielectric spectra of such composite systems are considerably modified compared to those of the corresponding pure LC or PMMA materials. The observed paraelectric to ferroelectric transition temperature of the composites is found to be lower (~ 85 °C) compared to that of the pure LC system (~ 98 °C), which makes these composites technologically more significant. The P–FLC composites also exhibit higher relaxation frequency and smaller dielectric strength for the Goldstone mode compared to those of the corresponding pure FLC. Depending on the percentage of the constitute materials, the molecular dynamics of the composite materials changes. Dielectric contributions of both liquid crystal and PMMA matrix forming the composites have been analyzed on the basis of Havriliak and Negami function.     

Thermoelectric Performance of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate)

Thermoelectric (TE) performances are systematically investigated for the pellets of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with different organic additives and heating process as organic TE materials. The electrical conductivity, Seebeck coefficient and thermal conductivity versus temperature are determined, respectively. It is found that there is no distinct change for the Seebeck coefficient among each sample with the additions of dimethyl sulfoxide and ethylene glycol. The thermal conductivity measured in a wide range of temperature indicates that the PEDOT:PSS pellet have an extremely low value. The highest figure of merit (Z_T= 1.75×10^-3) is observed at 270K among the PEDOT:PSS pellets.     

氧化铟/聚(3,4-乙烯二氧噻吩)复合材料的微结构及其热电性能研究

通过化学氧化合成的方法将纳米In_2O_3复合到聚(3,4-乙烯二氧噻吩)(PEDOT)中得到In_2O_3/PEDOT复合材料.利用X射线衍射、红外光谱、电子显微镜及正电子湮没等方法对复合材料的微观结构进行了系统研究,同时对材料的热学和电学性能进行了表征.结果表明,当In_2O_3的含量在22 wt%以下时,In_2O_3能很好地分散到PEDOT基体中.热电性能测试则显示In_2O_3/PEDOT复合材料的导电率随In_2O_3含量增加明显增大.纯PEDOT的电导率仅为7.5 S/m,而含12.3 wt%In_2O_3的复合材料的电导率达到25.75 S/m.该复合材料相应的功率因子(68.8×10~(-4)μW/m·K~2)相对于纯的PEDOT(14.5×10~(-4)μW/m·K~2)提高了近4倍.另外,复合材料的热导率相对于纯PEDOT也有所降低.最终复合材料的热电优值由0.015×10~(-4)提高到了0.073×10~(-4).结果表明,In_2O_3/PEDOT复合材料的热电性能相对于纯PEDOT的热电性能得到了比较明显的提高.     

Shape and magnetic moment dependence of the dipolar field in Mn_(12)-acetate

There is a small fraction of fast-relaxation species in Mn12-acetate, which is utilized to determine the dipolar field of Mn12. Here we report an easier way to precisely obtain the dipolar field by measuring the M-H curves above the blocking temperature of fastrelaxation species. We found that there is a simple linear relationship between the magnetic moment and dipolar field; besides the dipolar field is also dependent on the sample shape, which is consistent with the numerical calculation.     

Thermoelectric transport in conductive poly(3,4-ethylenedioxythiophene)

Poly(3,4-ethylenedioxythiophene)(PEDOT)has proved its quite competitive thermoelectric properties in flexible electronics with its excellent electrical and mechanical properties.Since the early discovery of PEDOT,considerable experimental progress has been achieved in optimizing and improving the thermoelectric properties as a promising organic thermoelectric material(OTE).Among them,theoretical research has made significant contributions to its development.Here the basic physics of conductive PEDOT are reviewed based on the combination of theory and experiment.The purpose is to provide a new insight into the development of PEDOT,so as to effectively design and preparation of advanced thermoelectric PEDOT material in the future.     

Effects of nanoparticle doping on the phase transitional behaviour of ferroelectric liquid crystal Langmuir–Blodgett composite films

Langmuir–Blodgett films of ferroelectric liquid crystals (FLCs) doped with a low concentration of functionalized Al: ZnO (AZO) nanoparticles were prepared and characterized. Pressure–area isotherms show that the nanoparticles as well as FLC composite systems have the capability to form stable monolayers at the air–water interface. The molecular interaction between nanoparticles and FLC molecules increased during barrier compression, which resulted in increased surface pressure. We observed various phases in isotherms with increasing concentration of nanoparticles in the FLC matrix. An X-ray diffraction profile at a low angle confirmed that FLCs retain their layer structure at a low concentration doping of AZO nanoparticles in the FLC matrix. Atomic force microscopy images indicate that low wt% composites are uniformly deposited without disturbing the translation behaviour of SmC* liquid crystals.     

Analysis of NMR shifts of high-spin cobalt(II) pyrazolylborate complexes

We present a detailed study on the correlation of the nuclear magnetic resonance (NMR) parameters with the results of density functional theory (DFT) calculations performed for paramagnetic high-spin cobalt(II) complexes with trispyrazolylborate ligands. This work is a first attempt to calculate dipolar and contact shifts in high-spin cobalt(II) pyrazolylborate systems. The calculation results show frontier orbitals that may be responsible for the contact shift. The contact shift values are compared with the dipolar shift ones. The latter shift values were both obtained from experimental data and calculated using DFT methods. We attempt to explain the dipolar effect, which may have a great share in NMR chemical shift of paramagnetic compounds.     

Chemical synthesis and characterization of poly(3,4-ethylenedioxythiophene)/tungsten composite materials in the presence of ionic liquids

Poly(3,4-ethylenedioxythiophene)/tungsten (PEDOT/W) composites were prepared by an in situ chemical oxidative polymerization of 3,4-ethylenedioxythiophene in different ionic liquids; 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆), 1-butyl- 3-methylimidazolium bis(trifluoromethylsulfonyl) imide (BMIMTFSI), and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide (BMPTFSI). These polymer/metal hybrids (PEDOT/W) were subsequently characterized for their structural, crystalline, thermal and morphological properties by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The significant enhancement in properties can be attributed to the nanoscale particle size and uniform size distribution of PEDOT/W and the synergistic effect between the inorganic nano-W and organic PEDOT material.     

石墨烯/聚乙撑二氧噻吩薄膜储能特性（英）

为了有效利用石墨烯和导电聚合物材料,光雕石墨烯/聚3,4-乙撑二氧噻吩(LSG/PEDOT)复合薄膜通过一种灵巧的光雕工艺制备出来。在此复合薄膜中,每种组分对薄膜的电化学性能提升都有独特的贡献。循环伏安、交流阻抗及恒流充放电测试用来检测薄膜的电化学性能。结果显示,在引入PEDOT纳米颗粒后,LSG/PEDOT复合薄膜显示出更好的能量存储能力。复合薄膜的比容量达到64.33 F/cm3,是光雕石墨烯比容量(3.89 F/cm3)的20倍,复合薄膜经过1000次循环后仍能保持初始容量的94.6%。复合薄膜电化学性能的提升主要是由于引入的PEDOT纳米颗粒既阻挡了石墨烯的层层堆叠,又增加了整个薄膜的比表面积。此种灵活的光雕工艺还可以用来大规模制备超级电容器电极。     

Modulating the Electrochromic Performances of Transmissive and Reflective Devices Using N,N-Dimethyl Formamide Modified Poly(3,4-Ethylenedioxythiophene)/Poly(Styrene Sulfonate) Blend as Active Layers

As one of the important factors which affect the properties and applications of conducting polymers, the electrical conductivity of a poly(3,4-ethylenedoxy-thiophene)/ poly(styrene sulfonate) (PEDOT: PSS) blend was adjusted by using various amount of an organic solvent (N,N-dimethyl formamide, DMF) as an additive. The conductivities of PEDOT: PSS thin films can be increased dramatically, from 1.0 S to 32.1 S cm^?1, with a 2/1 volume ratio of PEDOT: PSS/DMF loading after totally removing the organic solvent by annealing the film at 80° for 48 h in a vacuum oven. The optical contrasts of transmissive and reflective devices assembled using DMF-modified PEDOT: PSS as active layers exhibited a close relationship with the conductivity of PEDOT: PSS. Interestingly, high conductivity of PEDOT: PSS enhanced the contrast of a transmissive device, while high conductivity of PEDOT: PSS decreased the contrasts of a reflective device. The underlying reason is related to the different electrochromic mechanisms of these two types of device configurations.     

(1)H-(13)C INEPT MAS NMR correlation experiments with (1)H-(1)H mediated magnetization exchange to probe organization in lipid biomembranes

Two-dimensional (1)H-(13)C INEPT MAS NMR experiments utilizing a (1)H-(1)H magnetization exchange mixing period are presented for characterization of lipid systems. The introduction of the exchange period allows for structural information to be obtained via (1)H-(1)H dipolar couplings but with (13)C chemical shift resolution. It is shown that utilizing a RFDR recoupling sequence with short mixing times in place of the more standard NOE cross-relaxation for magnetization exchange during the mixing period allowed for the identification and separation of close (1)H-(1)H dipolar contacts versus longer-range inter-molecular (1)H-(1)H dipolar cross-relaxation. These 2D INEPT experiments were used to address both intra- and inter-molecular contacts in lipid and lipid/cholesterol mixtures.     

一种新方法制备硅/聚(3, 4-乙撑二氧噻吩)核/壳纳米线阵列杂化太阳能电池

采用气相聚合法制备了有机/无机杂化的硅/聚3, 4-乙撑二氧噻吩核/壳纳米线阵列(SiNWs/PEDOT)太阳能电池. 相对平面结构Si/PEDOT太阳能电池, SiNWs/PEDOT太阳能电池的能量转换效率提升了7倍, 达到3.23%.对比分析反射光谱、I-V曲线及外量子效率的实验结果, 发现SiNWs/PEDOT太阳能电池性能改进的主要原因可归结为: 气相聚合法能够有效地制备出SiNWs/PEDOT电池的核/壳纳米线阵列结构, 使得器件具有高光捕获、高比结面积和高电荷收集效率. 关键词： Si/PEDOT核/壳纳米线结构 太阳能电池 气相聚合     

Accurate measurement of H(N)-H(alpha) residual dipolar couplings in proteins.

A method for accurately measuring H(N)-H(alpha) residual dipolar couplings is described. Using this technique, both the sign and magnitude of the coupling can be determined easily. Residual dipolar coupling between H(N)(i)-H(alpha)(i) and H(N)(i)-H(alpha)(i-1) were measured for the FK506 binding protein complexed to FK506. The experimental values were in excellent agreement with predictions based on an X-ray crystal structure of the protein/ligand complex, suggesting that these residual dipolar couplings will provide accurate structural constraints for the refinement of protein structures determined by NMR.     

Dielectric and electro-optic behavior of pure ferroelectric liquid crystal material and the isomeric mixtures

We report here the dielectric relaxation spectroscopy and electro-optical properties of a ferroelectric liquid crystal (FLC) CB470 (R) and isomeric mixtures containing CB470 (R) and its optical isomer CB480 (S) in two different concentrations. We have studied with two isomeric mixtures: mixing CB470 (R) and CB480 (S) in the ratio 95:5 (w/w) and 90:10 (w/w). With increase of percentage of CB480 (S) in the mixture the spontaneous polarization (P_S) value has been decreased due to cancellation of a part of the dipolar contribution, since the direction of P_S of the two isomers are in opposite direction. The tilt angles of the pure FLC materials and the isomeric mixtures remain almost unchanged. The dielectric strength of Goldstone mode is almost proportional to the spontaneous polarization (P_S). An additional collective mode has been observed in the SmC¹ phase due to the formation of domain with large periodicity in pure FLC material and in one of the isomeric mixtures by unwinding the helical structures, which is known as domain mode. The existence of domain mode has been studied extensively with the variation of P_S in the isomeric mixtures. The result has been discussed.     

Frequency (250 MHz to 9.2 GHz) and viscosity dependence of electron spin relaxation of triarylmethyl radicals at room temperature

Electron spin relaxation times for four triarylmethyl (trityl) radicals at room temperature were measured by long-pulse saturation recovery, inversion recovery, and electron spin echo at 250 MHz, 1.5, 3.1, and 9.2 GHz in mixtures of water and glycerol. At 250 MHz T(1) is shorter than at X-band and more strongly dependent on viscosity. The enhanced relaxation at 250 MHz is attributed to modulation of electron-proton dipolar coupling by tumbling of the trityl radicals at rates that are comparable to the reciprocal of the resonance frequency. Deuteration of the solvent was used to distinguish relaxation due to solvent protons from the relaxation due to intra-molecular electron-proton interactions at 250 MHz. For trityl-CD(3), which contains no protons, modulation of dipolar interaction with solvent protons dominates T(1). For proton-containing radicals the relative importance of modulation of intra- and inter-molecular proton interactions varies with solution viscosity. The viscosity and frequency dependence of T(1) was modeled based on dipolar interaction with a defined number of protons at specified distances from the unpaired electron. At each of the frequencies examined T(2) decreases with increasing viscosity consistent with contributions from T(1) and from incomplete motional averaging of anisotropic hyperfine interaction.     

Poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) Zr(IV) phosphate composite cation exchanger : sol-gel synthesis and physicochemical characterization

An organic-inorganic composite cation exchanger poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) Zr(IV) phosphate was prepared by the sol-gel method for removal of cadmium, a toxic heavy metal pollutant causing adverse effects on human health. The synthesized material was characterized by various techniques such as thermo gravimetric analysis/differential thermal analysis/differential thermo gravimetry (TGA/DTA/DTG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). Organic polymer PEDOT:PSS binds with the inorganic counterpart and prevents the leaching of the inorganic parts, hence PEDOT:PSS Zr(IV) phosphate composite cation exchanger has improved ion exchange capacity than inorganic ion exchanger. The composite cation exchanger was found selective towards Cd(II) ions. The nature and composition of contacting solvents influence the selectivity of composite cation exchanger. The composite cation exchanger may be used for the removal of cadmium a toxic heavy metal ion.     

Measuring (13)C-(2)D dipolar couplings with a universal REDOR dephasing curve

A (13)C-observe REDOR experiment is described which allows (13)C-(2)D dipolar couplings to be obtained by a universal dipolar dephasing curve. Previous (13)C-observe REDOR experiments on (13)C-(2)D spin pairs generally relied on numerical simulations to obtain the dipolar coupling. The REDOR experiment described in this article is based on a deuterium composite pulse, and the data analysis eliminates the need for numerical simulations and is the same as the traditional REDOR analysis performed on pairs of spin-12 nuclei. Copyright 2000 Academic Press.