Tetrapropylammonium-manganese oxide/polypyrrole hybrid nanocomposite thin films as novel electrode materials for supercapacitors

Tetrapropylammonium-manganese oxide/polypyrrole (TPA-MO/Ppy) hybrid nanocomposite with molar ratios of TPA-MO/Ppy 4:1, 2:1 and 1:1 were successfully prepared by a combination of in situ polymerization and the sol–gel process. The microstructure of hybrid nanocomposite thin film samples was observed to be significantly affected by synthesis parameters, most notably the molar ratio of reactants and post-synthesis calcination temperature. Samples with higher pyrrole contents appeared to possess higher specific surface areas, which ranged from 132 to 281 m² g⁻¹. SEM micrographs indicated that all nanocomposite thin films were highly fibrous and porous in nature. Optimum doping of manganese oxide with conducting polypyrrole had led to the formation of novel nanocomposite with nanofibrillar structures which consisted of interconnected manganese oxide and polypyrrole nanoclusters. Optimized nanocomposite films showed higher charge capacities which could be attributed to enhanced material utilization as a result of optimized microstuctural parameters in particular, specific surface areas.     

Facile synthesis of carbon coated LiFePO4 nanocomposite with excellent electrochemical performance through in situ formed lithium stearate pyrolysis route

Carbon coated LiFePO₄ (LiFePO₄/C) nanocomposite is successfully synthesized at a comparatively low temperature (400 °C) via a pyrolysis process of in situ formed lithium stearate. The obtained products are characterized by X-ray diffraction, electron microscopy, thermogravimetry, infrared and X-ray photoelectron spectroscopy. Experimental results indicate that the in situ formed lithium stearate can decompose at ∼290 °C, which is beneficial for the formation of carbon coating and reduction of Fe³⁺ species, and then the crystallized LiFePO₄/C nanocomposite can be formed at 400 °C without other intermediate products. As cathode material of Li-ion battery, the obtained LiFePO₄/C nanocomposite exhibits a good rate and cycling performance with a high discharge capacity of ∼160 mAh g⁻¹ (>94% theoretical capacity of LiFePO₄) at a current density of 1 C (170 mA g⁻¹), and ∼96% of its initial capacity can be retained after 200 charging/discharging cycles. Even at a high current density (10 C), the LiFePO₄/C nanocomposite still presents a discharge capacity as high as ∼100 mAh g⁻¹. The excellent electrochemical performances of the present LiFePO₄/C nanocomposite mainly originate from the good crystallinity, small particles and enhanced electronic conductivity of the materials coated and linked by carbon layers.     

Fluorographene/polyimide composite films: Mechanical,electrical, hydrophobic,thermal and low dielectric properties

Nowadays, dielectric materials with excellent mechanical and hydrophobic properties are desired for use in the integrated circuits (ICs). For this reason, low dielectric constant fluorographene/polyimide (FG/PI) composite films were prepared by a facile solution blending method, suggesting that the mechanical, electrical, hydrophobic and thermal properties were significantly enhanced in the presence of FG. With addition of 1 wt% FG, the tensile strength, Young’s modulus and elongation at break were dramatically increased by 139%, 33% and 18% respectively when compared with pure PI film. Furthermore, composite films exhibit superior hydrophobic and thermal stability performance. Especially, the FG/PI film with 0.5 wt% of FG possessing a low dielectric constant of 2.48 and a good electrical insulativity that is lower than 10⁻¹⁴ S m⁻¹. Therefore, by their excellent performance, FG/PI hybrid films represent suitable candidate solutions with applications in the microelectronics and aerospace industries.     

Graphite oxide/poly(methyl methacrylate) nanocomposites prepared by a novel method utilizing macroazoinitiator

Graphite oxide (GO)/poly(methyl methacrylate) (PMMA) nanocomposites were prepared by a novel method utilizing macroazoinitiator (MAI). The MAI, which has a poly(ethylene oxide) (PEO) segment, was intercalated between the lamellae of GO to induce the inter-gallery polymerization of methyl methacrylate (MMA) and exfoliate the GO. The morphological, conductivity, thermal, mechanical and rheological properties of these nanocomposites were examined and compared with those of intercalated nanocomposites prepared by polymerization with the normal radical initiator, 2,2′-azobisisobutyronitrile. The improvement in conductivity by GO was more evident in exfoliated nanocomposites compared to that of intercalated nanocomposites. For example, a conductivity of 1.78 × 10⁻⁷ S/cm was attained in the exfoliated nanocomposite prepared with 2.5 parts GO per 100 parts MMA, which was about 50-fold higher than that of the intercalated nanocomposite. The thermal, mechanical and rheological properties also indicate that thin GO with a high aspect ratio is finely dispersed and effectively reinforced the PMMA matrix in both exfoliated and intercalated nanocomposites.     

Fluorinated graphene reinforced polyimide films with the improved thermal and mechanical properties

In order to explore the addition effect of fluorinated graphene (FG) on the mechanical and thermal performances of polyimide (PI) matrix, FG sheets are first prepared and employed as the nanofillers to construct PI/FG nanocomposite films. The prepared film is optically transparent at low content of FG and experimental results demonstrate that the addition of FG can effectively enhance the properties of PI matrix. Especially, compared with pure PI matrix, the addition of 0.5 wt% FG in PI can endow 30.4% increase in tensile stress and 115.2% increase in elongation at break. Experimental analyses considering the morphology and microstructure are also conducted, and the results indicate that the improved mechanical properties of the PI/FG nanocomposite films are mainly attributed to the good dispersibility of FG sheets in PI host, and the effective stress transfer between the polymer and the FG.     

Characterization and properties of in situ emulsion polymerized poly(methyl methacrylate)/graphene nanocomposites

Poly(methyl methacrylate) (PMMA)/graphene nanocomposites were prepared by in situ emulsion polymerization. Raman and Fourier transform infrared spectra showed that PMMA polymer contained partially reduced graphite oxide. Dynamic mechanical analysis and differential scanning calorimetry analysis showed that graphene in the PMMA matrix acted as reinforcing filler; it enhanced the storage moduli and glass transition temperatures of the nanocomposites. Thermogravimetric analysis showed that the thermal stability of the nanocomposites increased by ca. 35 °C. The electrical conductivity of nanocomposite with 3 wt.% graphite oxide was 1.5 S m⁻¹ at room temperature.     

A facile assembly of polyimide/graphene core–shell structured nanocomposites with both high electrical and thermal conductivities

Polyimide/reduced graphene oxide (PI/r-GO) core–shell structured microspheres were fabricated by in-situ reduction of graphene oxide (GO), which was coated on the surface of PI microspheres via hydrogen bonding and π–π stacking interaction. The highly ordered 3D core–shell structure of PI/r-GO microspheres with graphene shell thickness of 3 nm was well characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM) and Raman spectra. The glass transition temperature (T_g) of PI/r-GO microspheres was slightly increased because of the interaction of r-GO and PI matrix while the temperature at 5% weight loss (T_5%) of PI/r-GO microspheres was decreased due to the side effect of reductant hydrazine hydrate. The PI/r-GO nanocomposites exhibited highly electrical conductivity with percolation threshold of 0.15 vol% and ultimate conductivity of 1.4 × 10⁻² S/m. Besides, the thermal conductivity of PI/r-GO nanocomposites with 2% weight content of r-GO could reach up to 0.26 W/m K.     

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite based thin films for Schottky diode application

Transparent, conductive films of poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite were synthesized by in-situ oxidative polymerization and investigated for their Schottky diode property. The prepared films were characterized by UV–Vis spectroscopy, thermal gravimetric analysis (TGA), surface resistivity, cyclic voltametery, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). SEM reveals the formation of homogeneous and adhesive polymer films while HRTEM confirms the uniform wrapping of polymer chains around the nanotube walls for PEDOT-FWCNT film. Improved thermal stability, conductivity and charge storage property of PEDOT in the presence of FWCNT is observed. Among different compositions, 5 wt. % of FWCNT is found to be optimum with sheet resistance and transmittance of 500 Ω sq⁻¹ and 77%, respectively. Moreover, the electronic and junction properties of polymer films were studied and compared by fabricating sandwich type devices with a configuration of Al/PEDOT or PEDOT-FWCNT nanocomposite/indium tin oxide (ITO) coated glass. The measured current density-voltage characteristics show typical rectifying behavior for both configurations. However, enhanced rectification ratio and higher forward current density is observed in case of PEDOT-FWCNT based Schottky diode. Furthermore, reliability test depicts smaller hysteresis effect and better performance of PEDOT-FWCNT based diodes.     

Enhanced stress transfer and thermal properties of polyimide composites with covalent functionalized reduced graphene oxide

This work prepares (3-aminopropyl) trimethoxysilane (APTMS)-functionalized reduced graphene oxide (APTMS-rGO)/polyimide (PI) composite (APTMS-rGO/PI) through in-situ polymerization. NH₂-functionalized rGO coupled by APTMS demonstrates the good reinforced efficiency in mechanical and thermal properties, which is ascribed to the covalent-functionalized PI matrix by APTMS-rGO sheets. The uniform dispersion of APTMS-rGO increases the glass transition temperature (Tg) and the thermal decomposition temperature (Td), exhibiting 21.7 °C and 44 °C improvements, respectively. The tensile strength of the composites with 0.3 wt% APTMS-rGO is 31% higher than that of neat PI, and Young’s modulus is 35% higher than that of neat PI. Raman spectroscopy show the obvious G band shift, and also clearly demonstrates the enhanced interfacial interaction between rGO nanofillers and PI matrix. The high mechanical property of the APTMS-rGO/PI composites is attributed to the covalent functionalized GO by NH₂ groups and its good dispersion in comparison with GO.     

Cost-efficient high performance polyetheretherketone/expanded graphite nanocomposites with high conductivity for EMI shielding application

The cost efficient expanded graphite (EG) filled polyetheretherketone (PEEK) nanocomposites were prepared by hot pressing, which exhibited an electrical conductivity percolation threshold of 1.5 wt%. The electrical conductivity of the 1.5 wt% nanocomposite increased approximately eleven orders of magnitude than that of pure PEEK. The conductivities of 5 wt% and 10 wt% nanocomposites were increased to about 3.24 S cm⁻¹ and 12.3 S cm⁻¹, respectively. Scanning electron microscope showed 3-dimensional conductive network of EG across the PEEK matrix. The significant increase in electrical conductivity of the nanocomposites leads to the tremendous increase in electromagnetic interference shielding effectiveness.     

Effect of TiOx seed layer on the texture and electric properties in La and Ca modified PbTiO3 thin films

Lanthanum-and calcium-modified PbTiO₃ (PLCT) ferroelectric thin films were successfully prepared on Pt(111)/Ti/SiO₂/Si substrates by pulsed laser deposition. Influence of TiO_x seed layer on texture and electric properties of PLCT films was investigated. It is found the PLCT films without seed layer exhibited highly (100)-textured, while using about 9 nm TiO_x as seed layer lead to highly (301)-textured. The PLCT film with TiO_x seed layer possess higher remnant polarization (Pr = 26 µC/cm²), better pyroelectric coefficient and figure of merit at room temperature (p = 370 µC/m²k, F_d = 190 × 10^− 5 Pa^− 1/2) than that of film without seed layer. The mechanism of the enhanced electric properties was also discussed.     

Preparation of the acidic PVA/MMT nanocomposite polymer membrane for the direct methanol fuel cell (DMFC)

A novel nanocomposite polymer electrolyte membrane composed of PVA polymer matrix and nanosized Montmorillonite (MMT) filler, was prepared by a solution casting method. The characteristic properties of the PVA/MMT nanocomposite polymer membrane were investigated using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), atomic force microscopy (AFM), micro-Raman spectroscopy, and the AC impedance method. The PVA polymer directly blended with nanosized MMT filler (2-20 wt.%) showed good ionic conductivity, thermal, and mechanical properties. The highest ionic conductivity value for the acidic PVA/10 wt.%MMT nanocomposite polymer membrane was around 0.0368 S cm^− 1 at 30 °C. The methanol permeability (P) value was 3-4 × 10^− 6 cm² s^− 1. It was revealed that the addition of nanosized MMT fillers into the PVA matrix could markedly improve the electrochemical properties of the PVA/MMT nanocomposite membrane. In fact, the PVA/MMT nanocomposite polymer membrane appears to be a good candidate for the DMFC applications.     

Influence of reduced graphene oxide on mechanical behaviors of sodium carboxymethyl cellulose

Sodium carboxymethyl cellulose/reduced graphene oxide (NaCMC/rGO) nanocomposite films were prepared by a simple solution mixing-evaporation method. The NaCMC/rGO nanocomposite films were characterized and compared with sodium carboxymethyl cellulose/graphene oxide (NaCMC/GO) nanocomposite films. The stability of the rGO dispersion, and the structural and mechanical properties of the composite films were investigated by UV–Vis spectrophotometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and using a universal testing machine (UTM). The results revealed that CMC and rGO were able to form a homogenous mixture. Compared with pure CMC, the tensile strength and Young's modulus of the CMC/rGO nanocomposite films were considerably enhanced (by 72.52% and 131.79%, respectively) upon incorporation of 2 wt% rGO.     

Phosphorus-doped bismuth telluride films by electrodeposition

Phosphorus-doped Bi₂Te₃ films were synthesized on a stainless-steel electrode by electrochemical deposition. X-ray diffraction, scanning electron microscopy and transmission electron microscopy confirmed that the films are single-phased Bi₂Te₃ solid solutions with a rhombohedral structure. The as-prepared films exhibit n-type characteristics with the Hall coefficient −1.76E−2 m³ C⁻¹ and the electrical conductivity 280 S cm⁻¹. The thermal conductivity is 0.47 W m⁻¹ K⁻¹, which is as low as one-third of the value observed in the bulk material. The doped P atoms occupy the interstitial positions between the two adjacent Te(1) layers connected by Van der Waals interaction in Bi₂Te₃.     

Direct current electrical conduction mechanism in plasma polymerized thin films of tetraethylorthosilicate

The plasma polymerized tetraethylorthosilicate (PPTEOS) thin films were deposited on to glass substrates at room temperature by a parallel plate capacitively coupled glow discharge reactor. The current density-voltage (J-V) characteristics of PPTEOS thin films of different thicknesses have been observed at different temperatures in the voltage region from 0.2 to 15 V. In the J-V curves two slopes were observed — one in the lower voltage region and another in the higher voltage region. The voltage dependence of current density at the higher voltage region indicates that the mechanism of conduction in PPTEOS thin films is space charge limited conduction. The carrier mobility, the free carrier density and the total trap density have been calculated out to be about 2.80 × 10^− 15m²V^− 1s^− 1, 1.50 × 10²²m^− 3 and 4.16 × 10³³m^− 3 respectively from the observed data. The activation energies are estimated to be about 0.13 ± 0.05 and 0.46 ± 0.07 eV in the lower and higher temperature regions respectively for an applied voltage of 2 V and 0.09 ± 0.03 and 0.43 ± 0.10 eV in the lower and higher temperature regions respectively for an applied voltage of 14 V. The conduction in PPTEOS may be dominated by hopping of carriers between the localized states at the low temperature and thermally excited carriers from energy levels within the band gap in the vicinity of high temperature.     

Poly(vinyl alcohol) nanocomposite films containing chemically exfoliated molybdenum disulfide

Molybdenum disulfide (2H-MoS₂) was exfoliated in water after reaction with n-butyl-lithium. Using either alkaline or neutral conditions, different amounts of the resulting single-layer suspension were employed as filler for the production of poly(vinyl alcohol) films containing distinct disulfide contents. These nanocomposite films were obtained by wet casting and were further characterized by powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) and Raman spectroscopies. The mechanical properties of the films were also evaluated. Characterization studies revealed the attainment of homogeneous nanocomposite films in both alkaline and neutral conditions, indicating good distribution and interaction of the hydrophilic filler with the polyhydroxylated polymer. Improved Young's (tensile) modulus (+57%) and tensile strength (+9%) as well as reduced elongation (−78%) were achieved only when the neutral suspension of single layers was utilized. Increased MoS₂ content diminished the crystallinity of the polymer, while enhanced mechanical properties were obtained in the presence of intermediate filler content (around 1 wt%).     

Evaluation of microstructures and mechanical properties of diamond like carbon films deposited by filtered cathodic arc plasma

Diamond-like carbon (DLC) films were deposited by a cathodic arc plasma evaporation (CAPD) process, using a mechanical shield filter combined with a magnetic filter with enhanced arc structure at substrate-bias voltage ranging from − 50 to − 300 V. The film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). The mechanical properties were investigated by using a nanoindentation tester, scratch test and ball on disc wear test. The Raman spectra of the films showed that the wavenumber ranging from 900 to 1800 cm^− 1 could be deconvoluted into 1140 cm^− 1, D band and G band. The bias caused a significant effect on the sp³ content which was increased with the decreasing of I_D/I_G ratio. The XPS spectra data of the films which were etched by H⁺ plasma indicated the sp³ content are higher than those of the as-deposited DLC films. This implied that there is a sp²-rich layer present on the surface of the as-deposited DLC films. The nanoindentation hardness increased as the maximum load increased. A 380 nm thick and well adhered DLC film was successfully deposited on WC-Co substrate above a Ti interlayer. The adhesion critical load of the DLC films was about 33 N. The results of the wear tests demonstrated that the friction coefficient of the DLC films was between 0.12 and 0.2.     

Electrical transport mechanisms and photovoltaic behavior of 2-(2-furanylmethylene) propanedinitrile/p-Si heterojunction

Au/2-(2-furanylmethylene) propanedinitrile/p-Si heterojunction was fabricated using conventional thermal evaporation technique. Current density–voltage (J–V) characteristics of the heterojunction were investigated at different temperatures. Tunneling conduction mechanism in the lower voltage range was identified from the forward bias (J–V) characteristics. The calculated value of the change of built-in voltage with respect to the absolute temperature is (−1.88 × 10⁻³ V K⁻¹). At higher voltages, a space charge limited current (SCLC) mechanism controlled by an exponential trapping distribution above the valence band edge was observed. The total concentration of traps was found to be 8.077 × 10²¹ m⁻³. Under reverse bias, the conduction mechanism is due to thermally generated carriers in the lower voltage range and the Poole–Frenkel effect is observed in the higher voltage range. The heterojunction showed a photovoltaic behavior under illumination with an open-circuit voltage of 0.19 V and a short-circuit current density of 102.7 mA m⁻².     

Facile preparation and electrochemical characterization of graphene/ZnO nanocomposite for supercapacitor applications

Graphene/ZnO nanocomposites were successfully synthesized by microwave-assisted method. The structure, morphology, optical and composition of the obtained samples were characterized using XRD, FT-IR, laser Raman, UV–Vis spectroscopy and XPS analysis. XRD analysis confirmed the presence of graphene/ZnO nanocomposite. FE-SEM image reveals that the homogenous distribution of ZnO nanoparticles on the graphene nanosheets. The electrochemical properties of the graphene/ZnO electrodes were analyzed by cyclic voltammetry and impedance spectroscopy. The results confirmed that the incorporation of ZnO nanoparticles enhanced the capacitive performance of graphene electrode. Graphene/ZnO nanocomposite electrode showed higher capacitance value of 109 F g⁻¹ at a scan rate of 5 mV s⁻¹ in 1 M KCl solution as compared to the graphene electrodes. These results demonstrated the importance and great potential of graphene based composites in the development of high-performance energy-storage systems.     

Highly transparent o-PDA functionalized ZnS-polymer nanocomposite thin films with high refractive index

We prepared highly transparent nanocomposite films with high refractive index using fluorescent nanocrystal quantum dots (NQDs). The as synthesized transparent solution of ZnS NQDs was blended with poly(vinylpyrrolidone) (PVP) to prepare nanocomposite thin films. Morphological data, studied by atomic force microscopy (AFM) and X-ray diffraction (XRD), revealed that NQDs were impregnated with polymer matrix and the size distributions (3.0 ± 0.30 nm) of them were preserved in the composite films. The nanocomposite films show high optical transparency (T > 95% at 400 nm and T > 98.5% at 750 nm) and the refractive index is satisfactorily increased (1.565 at 550 nm, 15 wt.% ZnS) compared to the base polymer (1.480 at 550 nm). The nanocomposite films show defectless fluorescence emissions as observed from NQDs before impregnation.