Single-walled Carbon Nanotube Films Research Articles

Probing iodide/iodonium salt interactions with single-walled carbon nanotubes for resilient electrochemical capacitor

Self-standing films from single-walled carbon nanotubes (SWCNTs) were successfully used as electrochemical capacitors’ (ECs) electrode material, which exhibited state-of-the-art characteristics. The surface of SWCNTs was modified by iodonium salt molecules that substantially and permanently improved their electrical conductivity. The addition of pyridinium iodine chloride salt (IPyCl) quadrupled the value of the electrical conductivity of the SWCNT film, which reached values as high as 1022 S cm−1. Subsequently, the electrochemical performance of the newly designed self-standing SWCNTs with deposited IPyCl in aqueous neutral 1 M Li2SO4 and redox-active 1 M KI electrolytes was thoroughly analysed. Because redox activity of iodine species was observed mainly on the positive electrode, activated carbon with a developed surface area was used as a negative electrode to balance the faradaic charge. Due to the notable stability of iodonium salt dopant (instead of labile halogen-containing compounds typically used for SWCNT doping), robust charge/discharge performance of EC was demonstrated (> 10 000 cycles) in Li2SO4 electrolyte. Moreover, a significant improvement of capacitor metrics (from 49 to 75 F g−1) was obtained when electrodes modified by previously unexplored iodonium salt were utilized in 1 M KI electrolyte. Extensive analysis of the obtained data led to the elucidation of the doping mechanism responsible for the aforementioned achievements. The novel SWCNT-based electrodes enhanced with iodonium salt are auspicious materials, which can be used to build EC systems of appreciable capacitance.

Wide temperature range, air stable, transparent, and self-powered photodetectors enabled by a hybrid film of graphene and single-walled carbon nanotubes

Wide temperature range, air stable, transparent, and self-powered photodetectors enabled by a hybrid film of graphene and single-walled carbon nanotubes

High performance THz metasurface sensor based on modified-SWCNTs film for femtomolar protein detection

Terahertz (THz) metasurface sensor plays an important role in environmental monitoring, biomedical diagnostics, and materials science. However, most traditional THz metasurfaces for trace biological substance detection either suffer from high ohmic loss, or cannot achieve ultra-low concentration detection at the femtomolar level, which limits the application range of THz metasurfaces. Here, we propose a novel metasurface based on modified single-walled carbon nanotubes (SWCNTs) film for specific detection of SAA protein in femtomolar concentration. By modifying the SWCNTs film with concentrated sulfuric acid and introducing functionalized gold nanoparticles (Au-NPs), not only the non-resonant loss of the SWCNTs film was greatly reduced, but also the specific selection of trace SAA proteins was achieved. We experimentally demonstrated that the sensitivity of this THz metasurface sensor for SAA protein detection is 37.5 GHz/fM. In contrast to conventional metal or dielectric metasurfaces, because the unique mesh-like structure of the SWCNTs film can greatly increase the interaction between trace substances and the sensor, this new modifiable metasurface can achieve the lowest detection limit of 0.1fM, which has increased by an order of magnitude. Our results provide a new and promising method for THz metasurfaces to realize high-performance biosensors.

Self-powered PEDOT: PSS/CSWCNT/Mxenes Thermoelectric Films and Wearable Electronics Devices

In this work, Ti3C2-Cl is introduced into poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonic acid) / single-walled carbon nanotubes (PEDOT: PSS/SWCNT, noted as PPSC) films to prepare ternary thermoelectric films of PEDOT: PSS/SWCNT/Ti3C2-Cl (PPSCT). The microscopic morphology, structures, and thermoelectric properties of PPSC and PPSCT films show that the introduction of Ti3C2-Cl results in a tendency of decreasing electrical as well as thermal conductivity, and the Seebeck coefficient is increased. When the content of Ti3C2-Cl reaches 8 wt%, the conductivity, Seebeck coefficient, and thermal conductivity of the PPSCT films reach the optimum values of 1683 S/cm, 21.69 μV/K, and 14.97 W/mK, respectively, and the power factor (PF) and thermoelectric figure of merit (ZT) are 79.23 μW/mK2 and 1.58 × 10-3. The UPS and Hall effect results reveal that the improvement of the Seebeck effect of PPSCT mainly results from the ternary interfacial energy barrier as well as the change of carrier concentration. In addition, the wearable electronics devices demonstrate an output voltage of 4.5 mV and an output power of 54.36 nW under a 50 K temperature difference. The device displays a good monitoring sensitivity by reaching an output voltage of 0.6 mV at a 7 K temperature difference between the skin and the environment.

Boosting thermoelectric performance of single-walled carbon nanotubes-based films through rational triple treatments

Single-walled carbon nanotubes (SWCNTs)-based thermoelectric materials, valued for their flexibility, lightweight, and cost-effectiveness, show promise for wearable thermoelectric devices. However, their thermoelectric performance requires significant enhancement for practical applications. To achieve this goal, in this work, we introduce rational “triple treatments” to improve the overall performance of flexible SWCNT-based films, achieving a high power factor of 20.29 µW cm−1 K−2 at room temperature. Ultrasonic dispersion enhances the conductivity, NaBH4 treatment reduces defects and enhances the Seebeck coefficient, and cold pressing significantly densifies the SWCNT films while preserving the high Seebeck coefficient. Also, bending tests confirm structural stability and exceptional flexibility, and a six-legged flexible device demonstrates a maximum power density of 2996 μW cm−2 at a 40 K temperature difference, showing great application potential. This advancement positions SWCNT films as promising flexible thermoelectric materials, providing insights into high-performance carbon-based thermoelectrics.

Facile Lithium Densification Kinetics by Hyperporous/Hybrid Conductor for High-Energy-Density Lithium Metal Batteries.

Lithium metal anode (LMA) emerges as a promising candidate for lithium (Li)-based battery chemistries with high-energy-density. However, inhomogeneous charge distribution from the unbalanced ion/electron transport causes dendritic Li deposition, leading to "dead Li" and parasitic reactions, particularly at high Li utilization ratios (low negative/positive ratios in full cells). Herein, an innovative LMA structural model deploying a hyperporous/hybrid conductive architecture is proposed on single-walled carbon nanotube film (HCA/C), fabricated through a nonsolvent induced phase separation process. This design integrates ionic polymers with conductive carbon, offering a substantial improvement over traditional metal current collectors by reducing the weight of LMA and enabling high-energy-density batteries. The HCA/C promotes uniform lithium deposition even under rapid charging (up to 5mA cm-2) owing to its efficient mixed ion/electron conduction pathways. Thus, the HCA/C demonstrates stable cycling for 200 cycles with a low negative/positive ratio of 1.0 when paired with a LiNi0.8Co0.1Mn0.1O2 cathode (areal capacity of 5.0mAhcm-2). Furthermore, a stacked pouch-type full cell using HCA/C realizes a high energy density of 344Whkg-1 cell/951WhL-1 cell based on the total mass of the cell, exceeding previously reported pouch-type full cells. This work paves the way for LMA development in high-energy-density Li metal batteries.

Aerosol-Synthesized Surfactant-Free Single-Walled Carbon Nanotube-Based NO2 Sensors: Unprecedentedly High Sensitivity and Fast Recovery.

This study pioneers a chemical sensor based on surfactant-free aerosol-synthesized single-walled carbon nanotube (SWCNT) films for detecting nitrogen dioxide (NO2). Unlike conventional CNTs, the SWCNTs used in this study exhibit one of the highest surface-to-volume ratios. They show minimal bundling without the need for surfactants and have the lowest number of defects among reported CNTs. Furthermore, the dry-transferrable and facile one-step lamination resultsin promising industrial viability. When applied to devices, the sensor shows excellent sensitivity (41.6% at 500ppb), rapid response/recovery time (14.2/120.8s), a remarkably low limit of detection (below ≈0.161ppb), minimal noise, repeatability for more than 50 cycles without fluctuation, and long-term stability for longer than 6months. This is the best performance reported for a pure CNT-based sensor. In addition, the aerosol SWCNTs demonstrate consistent gas-sensing performance even after 5000 bending cycles, indicating their suitability for wearable applications. Based on experimental and theoretical analyses, the proposed aerosol CNTs are expected to overcome the limitations associated with conventional CNT-based sensors, thereby offering a promising avenue for various sensor applications.

Large-Area Flexible Carbon Nanofilms with Synergistically Enhanced Transmittance and Conductivity Prepared by Reorganizing Single-Walled Carbon Nanotube Networks.

Large-area flexible transparent conductive films (TCFs) are highly desired for future electronic devices. Nanocarbon TCFs are one of the most promising candidates, but some of their properties are mutually restricted. Here, a novel carbon nanotube network reorganization (CNNR) strategy, that is, the facet-driven CNNR (FD-CNNR) technique, is presented to overcome this intractable contradiction. The FD-CNNR technique introduces an interaction between single-walled carbon nanotube (SWNT) and Cu─-O. Based on the unique FD-CNNR mechanism, large-area flexible reorganized carbon nanofilms (RNC-TCFs) are designed and fabricated with A3-size and even meter-length, including reorganized SWNT (RSWNT) films and graphene and RSWNT (G-RSWNT) hybrid films. Synergistic improvement in strength, transmittance, and conductivity of flexible RNC-TCFs is achieved. The G-RSWNT TCF shows sheet resistance as low as 69Ωsq-1 at 86% transmittance, FOM value of 35, and Young's modulus of ≈45MPa. The high strength enables RNC-TCFs to be freestanding on water and easily transferred to any target substrate without contamination. A4-size flexible smart window is fabricated, which manifests controllable dimming and fog removal. The FD-CNNR technique can be extended to large-area or even large-scale fabrication of TCFs and can provide new insights into the design of TCFs and other functional films.

Evaluating the Efficiency of Boron Nitride Coating in Single-Walled Carbon-Nanotube-Based 1D Heterostructure Films by Optical Spectroscopy.

Single-walled carbon nanotube (SWCNT) films exhibit exceptional optical and electrical properties, making them highly promising for scalable integrated devices. Previously, we employed SWCNT films as templates for the chemical vapor deposition (CVD) synthesis of one-dimensional heterostructure films where boron nitride nanotubes (BNNTs) and molybdenum disulfide nanotubes (MoS2NTs) were coaxially nested over the SWCNT networks. In this work, we have further refined the synthesis method to achieve precise control over the BNNT coating in SWCNT@BNNT heterostructure films. The resulting structure of the SWCNT@BNNT films was thoroughly characterized using a combination of electron microscopy, UV-vis-NIR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and Raman spectroscopy. Specifically, we investigated the pressure effect induced by BNNT wrapping on the SWCNTs in the SWCNT@BNNT heterostructure film and demonstrated that the shifts of the SWCNT's G and 2D (G') modes in Raman spectra can be used as a probe of the efficiency of BNNT coating. In addition, we studied the impact of vacuum annealing on the removal of the initial doping in SWCNTs, arising from exposure to ambient atmosphere, and examined the effect of MoO3 doping in SWCNT films by using UV-vis-NIR spectroscopy and Raman spectroscopy. We show that through correlation analysis of the G and 2D (G') modes in Raman spectra, it is possible to discern distinct types of doping effects as well as the influence of applied pressure on the SWCNTs within SWCNT@BNNT heterostructure films. This work contributes to a deeper understanding of the strain and doping effect in both SWCNTs and SWCNT@BNNTs, thereby providing valuable insights for future applications of carbon-nanotube-based one-dimensional heterostructures.

Universal Sublimation Strategy to Stabilize Single-Metal Sites on Flexible Single-Wall Carbon-Nanotube Films with Strain-Enhanced Activities for Zinc-Air Batteries and Water Splitting.

Single-metal-site catalysts have recently aroused extensive research in electrochemical energy fields such as zinc-air batteries and water splitting, but their preparation is still a huge challenge, especially in flexible catalyst films. Herein, we propose a sublimation strategy in which metal phthalocyanine molecules with defined isolated metal-N4 sites are gasified by sublimation and then deposited on flexible single-wall carbon nanotube (SWCNT) films by means of π-π coupling interactions. Specifically, iron phthalocyanine anchored on the SWCNT film prepared was directly used to boost the cathodic oxygen reduction reaction of the zinc-air battery, showing a high peak power density of 247 mW cm-2. Nickel phthalocyanine and cobalt phthalocyanine were, respectively, stabilized on SWCNT films as the anodic and cathodic electrocatalysts for water splitting, showing a low potential of 1.655 V at 10 mA cm-2. In situ Raman spectra and theoretical studies demonstrate that highly efficient activities originate from strain-induced metal phthalocyanine on SWCNTs. This work provides a universal preparation method for single-metal-site catalysts and innovative insights for electrocatalytic mechanisms.

Ultrasensitive detection of miRNA based on single-walled carbon nanotube@MoS2 field-effect transistor regulated by atomic layer deposition

MicroRNAs (miRNAs) act as diagnostic markers for various diseases, and achieving ultra-sensitive detection of miRNAs has an important effect on early disease diagnosis. Field-effect transistor (FET) biosensor exhibits superior sensitivity compared to conventional clinical detection instruments in detecting biomolecules. However, developing high-sensitive FET biosensors for detecting microRNAs remains challenging. In this study, we developed a FET biosensor using MoS2 and a network film of semiconductor single-walled carbon nanotube (SWCNT) as channel materials. The MoS2 cycles were precisely controlled and optimized by atom layer deposition (ALD), and the optimized 3-cycle device exhibited the best performance. This adjustment is beneficial for enhancing the charge transfer between SWCNT and MoS2, as well as improving the on/off ratio and mobility of FET devices. Additionally, the SWCNT@MoS2 structure offers a larger specific surface area, providing more active binding sites on the sensing interface. These two favorable factors contribute to the realization of linear detection miRNA-21 from 1 × 10−17 to 1 × 10−10 mol L−1 in biosensors. The theoretical detection limit of the biosensor is 1.9 × 10−18 mol L−1. This work develops a novel approach to achieve highly sensitive detection of miRNA for high-performance FET biosensors.

Enhancing thermoelectric performance of single-walled carbon nanotube films by poly(styrene sulfonate acid) dispersing and sequential base treatment

Despite single-walled carbon nanotubes (SWCNTs) have attracted great interest for thermoelectric (TE) conversion, the strong van der Waals forces between SWCNTs cause them to aggregate into bundles with poor dispersibility, which dramatically deteriorates the charge carrier transport, and thereby induces low electrical conductivity and TE power factor. Herein, we report a facile and efficient approach to enhance TE performance of SWCNTs via the addition of poly(styrene sulfonic acid) (PSSH) and sequential base treatment. PSSH is served as a dispersant and dopant to improve the dispersibility of SWCNTs and facilitate charge carrier conduction, contributing to high electrical conductivity of 3749 ± 122 S cm−1 and power factor of 117.7 ± 3.4 μW m−1 K−2 for 20 wt% PSSH/SWCNT composite film. Further base treatment induces partial removal of insulative PSSH and de-doping effect of SWCNTs, which decreases the barriers between adjacent nanotubes junctions and modulates charge carrier transport to synergistically optimize the electrical conductivity and Seebeck coefficient. With fine-tuning base treatment temperature, the PSSH/SWCNT composite film reaches highest power factor of 160.6 ± 7.9 μW m−1 K−2, higher than pristine SWCNTs of 70.2 ± 4.4 μW m−1 K−2. This work demonstrates the feasibility of this approach to boost the TE properties of SWCNTs, exhibiting potential application for high performance renewable energy harvesting.

All-Automated Fabrication of Freestanding and Scalable Photo-Thermoelectric Devices with High Performance.

Flexible photo-thermoelectric (PTE) devices have great application prospects in the fields of solar energy conversion, ultrabroadband light detection, etc. A suitable manufacturing process to avoid the substrate effects as well as to create a narrow transition area between p-n modules for high-performance freestanding flexible PTE devices is highly desired. Herein, an automated laser fabrication (ALF) method is reported to construct the PTE devices with rylene-diimide-doped n-type single-walled carbon nanotube (SWCNT) films. Thewet-compressing approach is developed to improve the thermoelectric power factors and figure of merit (ZT) of the SWCNT hybrid films. Then, the films are cut and patterned automatically to make PTE devices with various structures by the proposed ALF method. The freestanding PTE device with a narrow transition area of ≈2-3 µm between the p and n modules exhibits a high-power density of 0.32 µW cm-2 under the light of 200 mW cm-2 , which is among the highest level for freestanding-film-based PTE devices. The results pave the way for the automatic production process of PTE devices for green power generation and ultrabroadband light detection.

Aligned and unaligned single-walled carbon nanotube bilayer films for uncooled infrared sensors

Semiconducting single-walled carbon nanotube (SWCNT) film fabrication using the dip-coating method has successfully produced a unique film with two layers of different morphologies, an upper layer of aligned SWCNT film and a lower layer of non-aligned SWCNT network film. In the upper layer, SWCNTs form SWCNT bundles of several SWCNT thicknesses, and the bundles form thin aligned SWCNT films of 2–7 nm in thickness with parallel and equally spaced bundles of SWCNTs. When a bolometer device with this bilayer film was fabricated on electrodes, the upper aligned SWCNT film was the main conductive path with a low resistivity of about 0.2 Ωcm around room temperature. The alignment film also achieved a high temperature coefficient of resistance (TCR) of more than −5%/K due to its thin thickness, which is hardly affected by the slight metallic SWCNT presence. These excellent properties of a high TCR and low resistance are advantageous for the development of innovative sensor elements.

Stable photothermal conversion in single-walled carbon nanotube device with pn-junction under uniform sunlight irradiation

N-type single-walled carbon nanotube (SWCNT) films with high air stabilities have attracted significant attention for their potential application in SWCNT devices featuring pn-junctions for power generation. However, SWCNT devices must be locally heated or formed into suspended structures to generate a temperature difference and produce output power. In this study, pn-junction SWCNT films were fabricated via vacuum filtration and subsequently attached to a polyimide substrate, enabling the creation of SWCNT devices without the need for suspended structures. Upon uniform irradiation with artificial sunlight, the SWCNT device produced a stable output voltage and short-circuit photocurrent. A thermographic image showed the emergence of a temperature gradient originating from the center of the SWCNT film and extending to the edge of the polyimide substrate. This phenomenon can be attributed to the higher optical absorption of SWCNT films compared to that of polyimide substrates. Consequently, the diffusion of carriers within the device generated an electric potential difference. Therefore, the SWCNT device generated a temperature gradient and yielded output power under uniform sunlight irradiation. These findings may aid in the development of facile and flexible optical devices, including photodetectors and hybrid devices integrating solar cells.

High figure-of-merit of single-walled carbon nanotubes films with metallic type conduction

Carbon nanotubes are promising candidates for thermoelectric power generation because of their one-dimensionality mediated high Seebeck coefficient, high electrical conductivity with added advantages of flexibility, light weight, and scalability. We report the temperature-dependent thermoelectric properties of single-walled carbon nanotube (SWCNTs) films. The SWCNTs films exhibit p-type metallic conduction with high Seebeck coefficient (∼69.5 μVK−1) and moderate electrical conductivity (∼76 Scm−1). The films exhibit low thermal conductivity (∼0.1 Wm−1 K−1) due to phonon scattering at the interjunction region. The synergetic combination of thermoelectric properties resulted in a high figure-of-merit of ∼0.11 at 305 K. A flexible thermoelectric generator based on SWCNTs films mounted on a curved hot surface exhibited an output of 17 mV and 54 μA under a small temperature gradient of 10 K. The present work provides possible avenues for developing wearable SWCNTs based thermoelectric power generation modules for harvesting body heat.

Fast liquid-free patterning of SWCNT films for electronic and optical applications

The development of new approaches to assembling carbon nanotubes in next-level architecture organization is one of the key directions in Nanomaterials Science. Meanwhile, the recent advances in the so-called rational design of thin single-walled carbon nanotube (SWCNT) films promise a significant improvement in the performance of electronic and optical devices. In this study, we propose a fast, efficient, and green method for the fabrication of 2D patterned SWCNT structures. This technique is based on the selective area deposition of SWCNTs synthesized in the aerosol (floating catalyst) CVD process. Such a liquid-free and one-step process beneficially distinguishes from existing alternative methods based on lithography on the filter or post-treatment lithography on already synthesized continuous films. We demonstrate a 12-fold improvement in the performance of patterned mesh-shaped SWCNT films used as transparent electrodes when compared to the continuous film. As a result, the sheet resistance at an overall 90 % transparency in the visible light range value of 62 Ω/□ was achieved. Moreover, transferred onto elastomer, the mesh-shaped SWCNT films were efficiently applied as tunable diffraction gratings in the THz range. We believe the technique proposed extends the possibilities of the aerosol CVD process for utilization in various applications.

Improved Heat Dissipation of Dip-Coated Single-Walled Carbon Nanotube/Mesh Sheets with High Flexibility and Free-Standing Strength for Thermoelectric Generators

Single-walled carbon nanotubes (SWCNTs) are promising thermoelectric materials used in thermoelectric generators (TEGs) to power sensors. However, the limitation of SWCNTs is their high thermal conductivity, which makes it difficult to create a sufficient temperature difference. In this study, we fabricated dip-coated SWCNT/mesh sheets using an SWCNT dispersion. Several types of mesh materials were tested, and the most suitable material was polyphenylene sulfide (PPS). SWCNTs were uniformly deposited on the PPS mesh surface without filling the mesh openings. The SWCNT/PPS mesh sheets exhibited flexibility and free-standing strength. When the edge of the SWCNT/PPS mesh sheets were heated, a higher temperature gradient was produced compared with that of the conventional SWCNT film owing to the increase in heat dissipation. A flexible and free-standing TEG with an area of 1200 mm2, fabricated using SWCNT/PPS mesh sheets, exhibited an output voltage of 31.5 mV and maximum power of 631 nW at a temperature difference of 60 K (Tlow: 320 K). When the TEG was exposed to wind at 3 m/s, temperature difference further increased, and the performance of the TEG increased by a factor of 1.3 for output voltage and 1.6 for maximum power. Therefore, we demonstrated that the TEG’s performance could be improved using SWCNT/PPS mesh sheets.

Narrow band absorption and sensing properties of single-walled carbon nanotubes at terahertz metasurface

Due to their excellent electrical and optical properties, carbon nanotubes have unique application prospects in the field of optoelectronics. In this work the vacuum self-assembly method is used to obtain an isotropic single-walled carbon nanotube film with a thickness of 2 μm by the dispersion of single-walled carbon nanotube powder through vacuum filtration; on the basis of extracting the dielectric parameters of the thin film in a range from 0.4 to 2.0 THz, a novel terahertz metasurface narrowband absorber based on single-walled carbon nanotube films is designed and prepared. This metasurface absorber is composed of square and I-shaped narrow slot resonators. The experimental and simulation results show that the proposed terahertz metasurface absorber exhibits four distinct resonance absorption peaks at 0.65, 0.85, 1.16, and 1.31 THz, respectively, achieving a perfect absorption of up to 90%. The absorption mechanism of this novel multi band terahertz metasurface is elucidated by using the theory of multiple reflection interference. By setting analytical layers with different refractive indices on the surface of metasurface device, the sensing performance of metasurface acting as refractive index sensor is studied in depth. The research results indicate that this new type of metasurface absorber has high sensitivity for refractive index sensing, providing new ideas and solutions for further developing carbon-based new terahertz metasurface absorbers.

A new type of portable pohotoelectrochemical sensor with polarity-switchable photocurrent for dopamine detection

The construction of accurate sensing method for dopamine (DA) is significant for the early diagnosis of some neurological diseases. Previous studies show that the concentration of DA in human body ranges from a few pM to several mM, depending on the sample species. Herein, a portable and sensitive photoelectrochemical (PEC) sensor for DA detection has been constructed, which is homogeneously deposited by thiophene-doped graphitic carbon nitride on the films of single-walled carbon nanotubes via vacuum filtration. In contrast to other PEC sensors for DA detections, our sensor shows polarity-switchable photocurrent with increasing DA concentration. Based on the polarity-switchable current response, the proposed PEC sensor exhibits good selectivity and a relatively wide detection range of 2.5-50 μM with the detection limit of 0.36 μM for DA. Furthermore, the applicability of the sensor was also tested for biological samples. The proposed PEC sensor holds much better potential applications in on-site disease monitoring.