This work describes the fabrication of poly(4-styrenesulfonic acid)-doped polyaniline/graphene (PSS-doped PANI/graphene) nanocomposites and their use as sensing elements for hydrogen sulfide (H2S) detection. PSS with a weight-average molecular weight (Mw) of 1.96 × 10(6) was synthesized using low-temperature free-radical polymerization. The PSS was used as both a doping agent and a binding agent for the polymerization of aniline monomers in a biphasic system (water-chloroform) at -50 °C. The high Mw of PSS resulted in relatively large particle sizes and smooth surfaces of the PSS-doped PANI. These physical characteristics, in turn, resulted in low interparticle resistance and high conductivity. In addition, the PSS allowed homogeneous dispersion of reduced graphene sheets through electrostatic repulsion. The prepared PSS-doped PANI/graphene solutions showed good compatibility with flexible poly(ethylene terephthalate) (PET) substrates, making them suitable for flexible sensor electrodes. Changes in the charge-transport properties, such as protonation level, conjugation length, crystalline structure, and charge-transfer resistance, of the electrode materials were the main factors influencing the electrical and sensor performance of the PSS-doped PANI-based electrodes. PSS-doped PANI/graphene composites containing 30 wt% graphene showed the highest conductivity (168.4 S cm(-1)) and the lowest minimum detection level (MDL) for H2S gas (1 ppm). This result is consistent with the observed improvements in charge transport in the electrode materials via strong π-π stacking interactions between the PANI and the graphene sheets.
Enhancement to the electrochemical performance of supercapacitor electrodes were realized by incorporating highly porous conductive polymer films prepared with solution-processed polyaniline. The resultant nanostructures contained characteristic pores measuring 30-150 nm. Such electrodes generated from a solution of polyaniline-camphorsulfonic acid (PANI/CSA) exhibited higher porosity and electro-catalytic activity than those generated from conventional PANI nanomaterials. These improvements were attributed to faster ion diffusion at the PANI electrode/electrolyte interface. The highest specific capacitance observed for a supercapacitor fabricated with a porous PANI electrode obtained was 361 F g(-1) at 0.25 A g(-1), which is more than twice that of an equivalent electrode made with pristine PANI. Furthermore, supercapacitors made with highly porous PANI electrodes exhibited high electrochemical stability and rate performances.
PSS/graphene surfaces facilitated redox reactions with the surrounding electrolyte, and significantly enhanced the specific capacitance of the electrode materials. The resulting RuO2/PEDOT:PSS/graphene electrode with a thickness of ∼5 μm exhibited high conductivity (1570 S cm(-1)), a large specific capacitance (820 F g(-1)), and good cycling stability (81.5% after 1000 cycles).
This work demonstrates a ternary nanocomposite system, composed of polypropylene (PP), redoped PANI (r-PANI) nanofibers, and reduced graphene oxides (RGOs), for use in a high energy density capacitor. r-PANI nanofibers were fabricated by the combination methods of chemical oxidation polymerization and secondary doping processes, resulting in higher conductivity (σ≈156 S cm(-1)) than that of the primarily doped PANI nanofibers (σ≈16 S cm(-1)). RGO sheets with high electron mobility and thermal stability can enhance the conductivity of r-PANI/RGO (σ≈220 S cm(-1)) and thermal stability of PP matrix. These findings could be extended to combine the advantages of r-PANI nanofibers and RGO sheets for developing an efficient means of preparing PP/r-PANI/RGO nanocomposite. When the r-PANI/RGO cofillers (10 vol %) were added to PP matrix, the resulting PP/r-PANI/RGO nanocomposite exhibited high dielectric constant (ε'≈51.8) with small dielectric loss (ε″≈9.3×10(-3)). Furthermore, the PP/r-PANI/RGO nanocomposite was used for an energy-harvesting device, which demonstrated high energy density (Ue≈12.6 J cm(-3)) and breakdown strength (E≈5.86×10(3) kV cm(-1)).
Microphones for hearing aid systems are required to have high sensitivity, an appropriate bandwidth, and a wide dynamic range. In this paper, a high sensitivity microphone, 4 mm in diameter and using a multilayer graphene-PMMA laminated diaphragm that can be applied in hearing aids, is designed, optimized, and implemented. Typically, polyphenylene sulfide (PPS) has been used for the diaphragm of electret condenser microphones (ECM), and this method provides simple, low cost mass production. Generally, the sensitivity of the commercial 4 mm diameter ECM is about -30 to 35 dB (0 dB = 1 V/Pa). A microphone using a nanometer-thick graphene diaphragm has been found to have higher sensitivity than the conventional ECM. However, nanometer-thick multilayer graphene is vulnerable to large mechanical shocks or high sound pressures, and the practical production of nanometer-thick diaphragms also poses a challenge. However, if a multilayer graphene diaphragm of the same thickness as the conventional ECM is used, displacement during diaphragm vibration will be severely attenuated due to the high elastic modulus of graphene, and the microphone sensitivity will be greatly reduced. In this paper, we fabricate a multilayer graphene/poly(methyl methacrylate) (PMMA) laminated diaphragm with sensitivity higher than that of any other microphones currently available for hearing aids, with the appropriate bandwidth in the auditory range. The high sensitivity arises from the laminated structure of the thin graphene membrane with high elastic modulus and from the PMMA membrane with lower elastic modulus and higher dielectric constant. The optimal thickness ratio of the graphene-PMMA layered diaphragm was studied by both analytical and experimental methods, and then a fabricated diaphragm was assembled in a 4 mm diameter microphone package. The performance of the implemented microphone was evaluated, including the sensitivity and total harmonic distortion. It is demonstrated that the microphone using a multilayer graphene-PMMA diaphragm has an excellent sensitivity of -20 dB and a dynamic range of 90 dB, which is on average 9 dB higher than the microphone using the conventional ECM diaphragm.
Highly conductive silica/polyaniline (PANi) core/shell nanoparticles (NPs) were synthesized in various diameters (from 18 to 130 nm) using self-stabilized dispersion polymerization. The polymerization was carried out in an aqueous/organic liquid system at -30 °C. In this system, the organic phase plays a key role in directing para-direction oriented polymerization of the PANi on the surface of silica NPs. Because of its para-direction polymerized structure, the synthesized silica/PANi core/shell NPs exhibited enhanced electrical conductivity (25.6 S cm(-1)) compared with NPs (1.4 S cm(-1)) prepared by homogeneous polymerization. The conductivities and BET surface areas were 25.6 S cm(-1)/170 m(2) g(-1) (18 nm in diameter), 22.5 S cm(-1)/111 m(2) g(-1) (35 nm in diameter), 18.3 S cm(-1)/78 m(2) g(-1) (63 nm in diameter), and 16.4 S cm(-1)/53 m(2) g(-1) (130 nm in diameter). In this series, increased para-coupling along the polymer backbone was elucidated using several characterization techniques, including Fourier transform infrared (FTIR), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR) spectroscopy. As-prepared silica/PANi core/shell NPs exhibited capacitance as high as 305 F g(-1).
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