Nowadays, flexible multifunctional composites are attracting much attention and are practically being used in various emerging electronic devices. However, most composites suffer from the disadvantages of high loadings of conductive fillers, complicated preparation processes, and low energy conversion efficiency. In this article, Caffeic acid-modified multiwalled carbon nanotubes (C-MWCNTs)/poly(3,4-ethylene dioxythiophene):polystyrene sulfonic acid (PEDOT:PSS)/polyimide (PI) composite films (CPFs) were prepared using a simple layer-by-layer deposition method. The "reinforced concrete" structure of the C-MWCNTs/PEDOT:PSS layer ensures high electrical conductivity of the film, while the PI layer provides excellent mechanical properties (72.69 MPa). The composite film exhibits excellent electrothermal response and thermal stability up to approximately 125 °C at 5 V. In addition, the good conductivity of the film provides its electromagnetic shielding effectiveness (32.69 dB). With these advantages, we expect that flexible CPFs will be widely utilized in wearable devices, electromagnetic interference (EMI) shielding applications, and thermal management of personal or electronic devices.
With the popularization of 5G technology and the development of science and technology, flexible and transparent conductive films (TCF) are increasingly used in the preparation of optoelectronic devices such as electromagnetic shielding devices, transparent flexible heaters, and solar cells. Silver nanowires (AgNW) are considered the best material for replacing indium tin oxide to prepare TCFs due to their excellent comprehensive properties. However, the loose overlap between AgNWs is a significant reason for the high resistance. This article investigates a sandwich structured conductive network composed of AgNW and Ti3C2Tx MXene for high-performance EMI shielding and transparent electrical heaters. Polyethylene pyrrolidone (PVP) solution was used to hydrophilic modify PET substrate, and then MXene, AgNW, and MXene were assembled layer by layer using spin coating method to form a TCF with a sandwich structure. One-dimensional AgNW is used to provide electron transfer channels and improve light penetration, while two-dimensional MXene nanosheets are used for welding AgNWs and adding additional conductive channels. The flexible TCF has excellent transmittance (85.1 % at 550 nm) and EMI shielding efficiency (27.1 dB). At the voltage of 5 V, the TCF used as a heater can reach 85.6 °C. This work offers an innovative approach to creating TCFs for the future generation.
Traditional conductive fabrics are prepared by the synthesis of conductive polymers and the coating modification of metals or carbon black conductive materials. However, the conductive fabrics cause a significant decline in performance after washing or mechanical wear, which limits their application. Moreover, the single function of the traditional conductive fabric is also the reason that limits its wide application. In order to prepare a wearable, stable, high-performance, washable, multifunctional conductive fabric, we have carried out related research. In this work, polydopamine was used as a bonding layer, an adsorption reduction layer, and a protective layer to improve the bonding between silver nanoparticles and carbon nanotubes (CNTs) on the polyester fabric surface so as to prepare a multifunctional conductive fabric with a high-stability "sandwich" structure, in which a Ag-NPS@CNT structure acting as an intermediate conductive layer formed on the inner layer PDA@CNT by electroless silver plating and the outermost layer PDA@CNT coated on the surface of the intermediate conductive layer by the impregnation-drying method. The sheet resistance of an E-Fabric can reach 2.11 Ω/â¡ due to the uniform and dense conductive path formed by the special structure Ag-NPs@CNT. At a low voltage of 1.5 V, the E-Fabric can reach 117 °C in 50 s and remain stable. The electrical conductivity and current heating properties of the E-Fabric remain good even after multiple washing or bending tests. Due to its stable and outstanding electrical conductivity, the E-Fabric has an electromagnetic shielding efficiency (SET) of 35.3 dB in the X-band (8.2-12.4 GHz). In addition, E-Fabric-based spin-coated poly(methyl methacrylate) or polydimethylsiloxane electrodes exhibit excellent performance in nanogenerators. Through the low-frequency friction of the human body, transient voltages up to 4 V can be generated from a 2 cm × 2 cm electrode sample. The output power of a single generator can reach about 12 nW/cm2. Therefore, an E-Fabric is considered to have great potential in the fields of electric heating, electromagnetic shielding, and smart wearable devices.
Transparent conductive films with high stability were prepared by embedding silver nanowires in colorless polyimide and adding a protective layer of exfoliated graphene. The films exhibit great light transmission and conductivity with a sheet resistance of 22 Ω sq-1at transmittance of 83%. Due to its special embedded structure, the conductive layer can withstand several peeling experiments without falling off. In addition, the most outstanding advantage is the ultra-high stability of the films, including high mechanical robustness, strong chemical corrosion resistance and high operating voltage capacity. The organic light-emitting diode devices prepared based on this transparent conductive electrode exhibit comparable efficiency to indium tin oxide (ITO) based devices, withC.E.max= 2.78 cd A-1,P-1.E.max= 1.89 lm W-1,EQEmax= 0.89%. Moreover, the efficiencies were even higher than that of ITO devices when the operating voltage of the device exceeds 5 V. The above performances show that the transparent conductive electrode based on this structure has high potential for application in organic electronic devices.
Recently, the electronic waste (E-waste) has become the most serious environmental trouble because of the iteration of electronic products. Transparent conductive films (TCFs) are the key component of flexible electronic devices, so the development of devices based on degradable TCFs has become an important way to alleviate the problem of E-waste. Gelatin, one of the most prevalent natural biomacromolecules, has drawn increasing attention due to its good film-forming ability, superior biocompatibility, excellent degradability, and commercial availability at a relatively low cost, but has few applications in flexible electronics. Here, we report a method for preparing flexible TCF based on naturally degradable material-fish gelatin, in which silver nanowires and Ti3C2Tx flakes were used as conductive fillers. The obtained TCF has low roughness (RMS roughness = 5.62 nm), good photoelectric properties (Rs = 25.2 Ω/sq., T = ca.85% at 550 nm), strong interfacial adhesion and good degradability. Moreover, the film showed excellent application in the field of EMI shielding and green light OLED device. We believe that these TCFs will shine in the smart wearable field in the future.
Improved OLED systems have great potential for next-generation display applications. Carbon nanotubes (CNTs) and the conductive polymers poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT: PSS) have attracted great interest for advanced applications, such as optoelectronic products. In this paper, the simultaneous enhancement of the conductivity, roughness, and adhesion properties of transparent conductive films with PEDOT: PSS/CNTs is reported. These films prepared by a simple spin-coating process were successfully used to produce high-performance organic light-emitting diodes (OLEDs) with an improved lifetime. Addition of PEDOT: PSS lowered the film sheet resistance and CNTs helped to enhance the stability and maintain the lifetime of the OLEDs. In addition, treatment with methanol and nitric acid changed the morphology of the polymer film, which led to greatly reduced sheet resistance, enhanced substrate adhesion, and reduced film roughness. The best performance of the film (PEDOT: PSS: CNT = 110: 1, W/W) was 100.34 Ω/sq.@ 90.1 T%. High transmittance, low sheet resistance, excellent adhesion, and low roughness (3.11 nm) were achieved synchronously. The fabricated OLED demonstrated a low minimum operating voltage (3 V) and could endure high voltage (20 V), at which its luminance reached 2973 cd/m2. Thus, the incorporation of CNTs within PEDOT: PSS electrodes has great potential for the improvement of the performance of OLED devices.
Graphene film has wide applications in optoelectronic and photovoltaic devices. A novel and facile method was reported for the reduction of graphene oxide (GO) film by electron transfer and nascent hydrogen produced between aluminum (Al) film deposited by magnetron sputtering and hydrochloric acid (HCl) solution for only 5 min, significantly shorter than by other chemical reduction methods. The thickness of Al film was controlled utilizing a metal detection sensor. The effect of the thickness of Al film and the concentration of HCl solution during the reduction was explored. The optimal thickness of Al film was obtained by UV-Vis spectroscopy and electrical conductivity measurement of reduced GO film. Atomic force microscope images could show the continuous film clearly, which resulted from the overlap of GO flakes, the film had a relatively flat surface morphology, and the surface roughness reduced from 7.68 to 3.13 nm after the Al reduction. The film sheet resistance can be obviously reduced, and it reached 9.38 kΩ/sq with a high transmittance of 80% (at 550 nm). The mechanism of the GO film reduction by electron transfer and nascent hydrogen during the procedure was also proposed and analyzed.
Graphene oxide (GO), reduced graphene oxide (rGO) and carbon nanotubes (CNTs) have their own advantages in electrical, optical, thermal and mechanical properties. An effective combination of these materials is ideal for preparing transparent conductive films to replace the traditional indium tin oxide films. At present, the preparation conditions of rGO are usually harsh and some of them have toxic effects. In this paper, an SnCl2/ethanol solution was selected as the reductant because it requires mild reaction conditions and no harmful products are produced. The whole process of rGO preparation was convenient, fast and environmentally friendly. Then, SEM, XPS, Raman, and XRD were used to verify the high reduction efficiency. CNTs were introduced to improve the film conductive property. The transmittance and sheet resistance were the criteria used to choose the reduction time and the content ratios of GO/CNT. Thanks to the post-treatment of nitric acid, not only the by-product (SnO2) and dispersant in the film are removed, but also the doping effect occurs, which are all conducive to reducing the sheet resistances of films. Ultimately, by combining rGO, GO and CNTs, transparent conductive films with a bilayer and three-dimensional structure were prepared, and they exhibited high transmittance and low sheet resistance (58.8 Ω/sq. at 83.45 T%, 47.5 Ω/sq. at 79.07 T%), with corresponding [Formula: see text] values of 33.8 and 31.8, respectively. In addition, GO and rGO can modify the surface and reduce the film surface roughness. The transparent conductive films are expected to be used in photoelectric devices.
In this paper, we used tannic acid (TA) functionalized carbon nanotubes (TCNTs), and silver nanowires (AgNWs) to construct a new type of transparent conductive film (TCF) with a double-layered conductive network structure. The hybrid film exhibits excellent light transmittance, high electrical conductivity, ultra-flexibility, and strong adhesion. These outstanding performances benefit from the filling and adhesion of hydrophilic TCNT layers to the AgNW networks. Besides, we introduced the post-treatment process of mechanical pressing and covering polymer conductive polymer PEDOT:PSS, which obtained three layers of TCNT/AgNW/PEDOT hybrid film and greatly improved the comprehensive properties. The hybrid film can reach a sheet resistance of 9.2 Ω sq-1 with a transmittance of 83.4% at 550 nm wavelength, and a low root mean square (RMS) roughness (approximately 3.8 nm). After 10 000 bends and tape testing, the conductivity and transmittance of the hybrid film remain stable. The resistance of the film has no significant degradation after 14 d of exposure to high temperature of 85 °C and humidity of 85%, indicating excellent stability. The organic light-emitting diodes (OLEDs) with TCNT/AgNW/PEDOT hybrid film as anode exhibit high current density and luminosity, confirming this process has considerable potential application in photovoltaic devices.
In this paper, the eco-friendly plant polyphenol, tannic acid (TA) was demonstrated as a non-covalent modifier for carbon nanotubes (CNTs), as well as a stripping medium to achieve exfoliated graphite to graphene by microfluidization. High-performance transparent flexible heater (TFH) with an embedded structure had been successfully fabricated by integrating conductive nanocomposites (TA-functionalized grapheme/TA-functionalized CNT/PEDOT:PSS; TG/TCNT/PEDOT) into waterborne polyurethane (WPU) film. Such a film exhibited favorable optical transmittance and sheet resistance (T = ca. 80% at 550 nm, Rs = 62.5 Ω/sq.), low root mean square (rms) roughness (approximately 0.37 nm), excellent adhesion and mechanical stability (the sheet resistance remained almost constant after 1000 bending cycle test for the bending radius of 10 mm), which are ideal as transparent heaters with high thermal efficiency. For TG/TCNT/PEDOT-WPU TFHs, the temperature increased rapidly and reached a steady state within 20 s with the maximum temperature reached to 116 °C, when the applied voltage was 20 V. Moreover, no variation in temperature was observed after the repeated heating-cooling tests and long-time stability test, indicating that TG/TCNT/PEDOT-WPU TCFs can be used as high performance TFHs. These TFH's are expected to be suitable for vehicle defrosting, smart windows, portable heating, smart wearable devices, etc.
Membrane fouling can be effectively addressed by modifying the membrane to realize anti-fouling capability together with real-time fouling detection. Here, we present the synthesis and water treatment testing of a promising candidate for this application, a composite membrane of polyvinylidene fluoride (PVDF) and functionalized carbon nano-materials prepared by a facile phase inversion method. The synergistic effect of oxidized multi-walled carbon nanotubes (OMWCNTs) and graphene oxide (GO) enabled better surface pore structures, higher surface roughness, hydrophilicity, and better antifouling property as compared with that of pristine PVDF membranes. The PVDF/OMWCNT/GO mixed matrix membranes (MMMs) achieved a high water flux of 125.6â¯Lâ¯m-2â¯h-1 with high pollutant rejection rate, and their electrical conductivity of 2.11â¯×â¯10-4â¯Sâ¯cm-1 at 100â¯kHz was sensitive to the amount of pollutant uptake. By using hybrid MMMs, we demonstrate simultaneous pollutant filtering and uptake monitoring, which is an important step in revolutionizing the water treatment industry.
The amphiphilic graphene derivative was prepared by covalent grafting of graphene oxide (GO) with isophorone diisocyanate and N,N-dimethylethanolamine and then noncovalent grafting of GO with sodium dodecylbenzenesulfonate. The results obtained from infrared spectroscopy, X-ray photoelectron spectroscopy, thermal gravimetric analysis, and X-ray diffraction analysis revealed that the short chains were successfully grafted onto the surface of GO. Subsequently, scanning electron microscopy and optical microscopy results showed that the modified GO (IP-GO) has the best dispersibility and compatibility than GO and reduced GO in the waterborne polyurethane matrix. The relationship between the corrosion resistance of composite coatings and the dispersibility of the graphene derivative and the compatibility of the graphene derivative with a polymer matrix were discussed. The anticorrosive properties were characterized by electrochemical impedance spectroscopy analysis and salt spray tests. Through a series of anticorrosion tests, it is concluded that the anticorrosion performance of a composite coating with 0.3 wt % IP-GO is significantly improved. The excellent anticorrosion performance is due to the perfect dispersion and good compatibility of IP-GO in waterborne polyurethane.
Transparent conductive films (TCFs) were fabricated via a spray-coating method with a solution prepared by dispersing single-walled carbon nanotubes (SWCNTs) in deionized water with sodium dodecylbenzene sulfonate (SDBS) as surfactant. We explored the mechanism of HNO3 treatment by treating TCFs with different reagents. After being treated with different concentrations of reagents by HNO3, HCl, and NaNO3 to lower the sheet resistance of TCFs, the properties of TCFs were further characterized by a UV-VIS spectrophotometer, a four-point probe method, atom force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. In this study, we conclude that the HNO3 treatment results in a decrease in the sheet resistance of the TCFs due to the combined effect of acidity and oxidizability. The strong interaction of the strong acidity and strong oxidizing property of HNO3 causes the SDBS to be removed. To further improve the film conductivity of the TCFs, the experimental conditions of the HNO3 treatment were optimized.
High-performance, flexible film heaters with carbon nanotube transparent conducting films are easily fabricated by both a rod-coating method and a spraying method. The main conclusion we have reached is that the film demonstrates a heating rate of 6.1°C s-1 at 35 V and sheet resistance as low as 94.7 Ω sq-1 with 72.04% optical transmittance at a wavelength of 550 nm by the spraying method after a series of post-treatment processes with acid and distilled water. Then, we adopt a mathematical method of nonlinear fitting to simulate the collected experimental data and the functions effectively. Furthermore, through analysis of the formula, the correlation between temperature and time is well explained. Therefore, carbon nanotube-based, flexible, transparent heaters exhibit high electrothermal performance and are expected to find different applications, e.g. various functional devices such as heating materials, heatable smart windows or dining tables.
Novel hierarchical chrysanthemum-flower-like carbon nanomaterials (CFL-CNMs) were synthesized by thermal chemical vapor deposition based on acetylene decomposition. A scanning electron microscope and a transmission electron microscope were employed to observe the morphology and structure of the unconventional nanostructures. It is found that the CFL-CNMs look like a blooming chrysanthemum with a stem rather than a spherical flower. The carbon flower has an average diameter of 5 µm, an average stem diameter of 150 nm, branch diameters ranging from 20 to 70 nm, and branch lengths ranging from 0.5 to 3 µm. The morphologies of the CFL-CNMs are unlike any of those previously reported. Fishbone-like carbon nanofibers with a spindle-shaped catalyst locating at the tip can also be found. Furthermore, the catalyst split was proposed to elucidate the formation mechanism of CFL-CNMs. A large and glomerate catalyst particle at the tip of the carbon nanofiber splits into smaller catalyst particles which are catalytic-active points for branch formation, resulting in the formation of CFL-CNMs.
Graphene oxide nanosheets (GONSs) with a lateral size less than 100 nm have attracted more and more attention for their wide range of potential applications, from bionanotechnology and nanobiomedicine to surfactants. However, at present GONSs are commonly prepared from graphite nanofibers or graphite nanopowders which are both expensive. Here, a timesaving, low-cost, high-yield method is proposed for preparing ultrasmall uniform GONSs with an average lateral size of â¼30 nm, utilizing common graphite powder as the raw material in the absence of a strong acid. The obtained GONSs are able to disperse single-walled carbon nanotubes (SWCNTs) effectively, and the dispersion could withstand high-speed centrifugation. Consequently, GONSs could indeed serve as a superior surfactant for the dispersion of SWCNTs, and the dispersion could be further applied in electronics, as the GONSs may be further reduced to reduced GONSs or graphene nanosheets.
Y-junction carbon nanocoils (Y-CNCs) were synthesized by thermal chemical vapor deposition using Ni catalyst prepared by spray-coating method. According to the emerging morphologies of Y-CNCs, several growth models were advanced to elucidate their formation mechanisms. Regarding the Y-CNCs without metal catalyst in the Y-junctions, fusing of contiguous CNCs and a tip-growth mechanism are considered to be responsible for their formation. However, as for the Y-CNCs with catalyst presence in the Y-junctions, the formation can be ascribed to nanoscale soldering/welding and bottom-growth mechanism. It is found that increasing spray-coating time for catalyst preparation generates agglomerated larger nanoparticles strongly adhering to the substrate, resulting in bottom-growth of CNCs and appearance of the metal catalyst in the Y-junctions. In the contrary case, CNCs catalyzed by isolated smaller nanoparticles develop Y-junctions with an absence of metal catalyst by virtue of weaker adhesion of catalyst with the substrate and tip-growth of CNCs.
Single-walled carbon nanotube (SWCNT) transparent conducting films (TCFs) were fabricated for the electrodes of organic light-emitting diodes (OLEDs); three types of film were studied. The as-prepared SWCNT TCFs displayed a relatively low sheet resistance of 82.6 Ω/sq at 80.7 T% with a relatively large surface roughness of 30 nm. The TCFs were top-coated with poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) to obtain PEDOT:PSS-coated TCFs. The PEDOT:PSS cover improved the conductivity and decreased the surface roughness to 12 nm at the cost of film transmittance. The SWCNT TCFs mixed with PEDOT:PSS (PM-TCFs) exhibited a high conductivity (70.6 Ω/sq at 81 T%) and a low surface roughness (3 nm) and were thus selected as the best TCFs for OLEDs. Blue flexible OLEDs with 4,4'-bis(2,2'-diphenylvinyl)-1,1'-biphenyl (Dpvbi) as the emitting layer were fabricated on TCFs with the same structures to evaluate the performances of the different types of SWCNT films for use in OLEDs. Of these three types of OLEDs, the PM-TCF devices exhibited the optimal performance with a maximum luminance of 2587 cd m(-2) and a current efficiency of 5.44 cd A(-1). This result was explored using field-emission scanning electron microscopy and atomic force microscopy to further study the mechanisms that are involved in applying SWCNT TCFs to OLEDs.
We investigated the modulation of optical properties of single-walled carbon nanotubes (SWCNTs) by AuCl 3 doping. The van Hove singularity transitions (E 11 (S), E 22 (S), E 11 (M)) in absorption spectroscopy disappeared gradually with an increasing doping concentration and a new peak appeared at a high doping concentration. The work function was downshifted up to 0.42 eV by a strong charge transfer from the SWCNTs to AuCl 3 by a high level of p-doping. We propose that this large work function shift forces the Fermi level of the SWCNTs to be located deep in the valence band, i.e., highly degenerate, creating empty van Hove singularity states, and hence the work function shift invokes a new asymmetric transition in the absorption spectroscopy from a deeper level to newly generated empty states.
Oxydianiline-pyromellitic dianhydride poly(amic acid) (ODA-PMDA PAA) was polymerized with a catalyst support of triethyl amine for controlling molecular weight. This polymer was used for electrospinning in the preparation of PAA nanofibers, a precursor of carbon nanofibers. Here the amount of catalyst and concentration of PAA solution were optimized to produce polyimide-based carbon nanofibers approximately 80 nm in diameter. The effects of molecular weight of PAA, bias voltage, and spinning rate on the morphology of electrospun PAA and polyimide nanofibers have been evaluated. We showed that the conductivity of the carbon nanofiber mat decreased with increasing nanofiber diameter, where the conductivity of polyimide-based carbon nanofiber mat was much higher than those of other types of carbon nanofiber mat. The key ingredient to increase conductivity in a carbon nanofiber mat was found to be the number of cross junctions between nanofibers.
