High-Performance Structural Supercapacitors Based on Aligned Discontinuous Carbon Fiber Electrodes and Solid Polymer Electrolytes.

This paper presents an investigation of the potential to use aligned discontinuous carbon fiber dry prepregs as electrodes in structural supercapacitors (SSCs). The high fiber-matrix interfacial bonding of the structural composite was achieved by adopting a solid polymer electrolyte, consisting of poly(vinylidene), lithium triflate, and epoxy. Processing of the SSC was carried out via dip-coating of the polymer electrolyte and then cured using a vacuum bag. The electrochemical performance of the SSCs was measured before and after mechanical loading. The microstructures of the SSCs as-fabricated and damaged under flexural loading were identified by µ-CT imaging. An SSC with a specific capacitance of 0.128 mF/cm2 (11.62 mF/g), a flexural strength of 47.49 MPa, and a flexural modulus of 8.48 GPa has been achieved, demonstrating significant improvements in mechanical properties over those of SSCs based on woven carbon fiber fabric-based electrodes. The mechanical behavior of the supercapacitors was evaluated by both quasi-static and cyclic flexural loading tests. The excellent electrochemical stability of the supercapacitors was validated by a capacitance retention of above 96% under galvanostatic charge-discharge cycling tests. The knowledge gained in this work will benefit future research in the optimization of SSC performance.

Sensitivity Improvement of Stretchable Strain Sensors by the Internal and External Structural Designs for Strain Redistribution.

Fiber strain sensors that are directly woven into smart textiles play an important role in wearable systems. These sensors require a high sensitivity to detect the subtle strain in practical applications. However, traditional fiber strain sensors with constant diameters undergo homogeneous strain distribution in the axial direction, thereby limiting the sensitivity improvement. Herein, a novel strategy of internal or external structural design is proposed to significantly improve the sensitivity of fiber strain sensors. The fibers are produced with directional increases in diameter (internal design) or polydimethylsiloxane (PDMS) microbeads attached to surfaces (external design) by combining hollow glass tubes used as templates with PDMS drops. The structural modification of the fiber significantly impacts the sensing performance. After optimizing structural parameters, the highest gauge factor reaches 123.1 in the internal-external structure design at 25% strain. A comprehensive analysis reveals that the desirable scheme is the internal structural design, which features a high sensitivity of 110 with a 100% improvement at ∼5-20% strain. Because of the sufficiently robust interface, even at the 800th cycle, fiber sensors still possessed an excellent stable performance. The morphology evolution mechanism indicates that the resistance increase is closely related with the increased peak width and distance, and the appearance of gaps. Based on the finite element modeling simulation, the quantified effective contributions of different strategies positively correlate with the improved sensitivity. The proposed fiber strain sensors, which are woven into the two-dimensional network structure, exhibit an excellent capability for displacement monitoring and facilitate the traffic control of crossroads.

Low Tortuous, Highly Conductive, and High-Areal-Capacity Battery Electrodes Enabled by Through-thickness Aligned Carbon Fiber Framework.

Thick electrode with high-areal-capacity is a practical and promising strategy to increase the energy density of batteries, but development toward thick electrode is limited by the electrochemical performance, mechanical properties, and manufacturing approaches. In this work, we overcome these limitations and report an ultrathick electrode structure, called fiber-aligned thick or FAT electrode, which offers a novel electrode design and a scalable manufacturing strategy for high-areal-capacity battery electrodes. The FAT electrode uses aligned carbon fibers to construct a through-thickness fiber-aligned electrode structure with features of high electrode material loading, low tortuosity, high electrical and thermal conductivity, and good compression property. The low tortuosity of FAT electrode enables fast electrolyte infusion and rapid electron/ion transport, exhibiting a higher capacity retention and lower charge transfer resistance than conventional slurry-casted thick electrode design.

Wet-spinning assembly and in situ electrodeposition of carbon nanotube-based composite fibers for high energy density wire-shaped asymmetric supercapacitor.

Wire-shaped supercapacitors (WSC) have attracted tremendous attention for powering portable electronic devices. However, previously reported WSC suffered from a complicated fabrication process and high cost. The objective of this study is to develop a facile and scalable process for the fabrication of high energy density WSC. We coupled the wet-spinning assembly with an in situ electrodeposition technique to prepare carbon nanotube (CNT)-based composite fibers. The charge balance between the electrodes was realized by controlling the deposition time of the pseudocapacitive materials. A wire-shaped asymmetric supercapacitor (WASC) was fabricated by twisting MnO2/CNT fiber cathode and PPy/CNT fiber anode with LiCl/PVA electrolyte. The flexible MnO2/CNT//PPy/CNT WASC operated in a broadened voltage range of 0-1.8 V exhibited a high capacitance of 17.5F cm-3 (10.7F g-1). In addition, it delivered a maximum energy and power densities of 7.88 mWh cm-3 (4.82 Wh kg-1) and 2.26 W cm-3 (1382 W kg-1), respectively. The WASC device demonstrated satisfactory cycling stability with 86% capacitance retention, and its Coulombic efficiency remained at 96% after 5000 charge-discharge cycles. The contributions of the diffusion-controlled insertion and the surface capacitive effect were theoretically quantified to investigate the energy storage mechanism. The fabrication approaches hold potential for the construction of cost-effective and high-performance WSC.

Highly stretchable multi-walled carbon nanotube/thermoplastic polyurethane composite fibers for ultrasensitive, wearable strain sensors.

Here, we report a novel highly sensitive wearable strain sensor based on a highly stretchable multi-walled carbon nanotube (MWCNT)/Thermoplastic Polyurethane (TPU) fiber obtained via a wet spinning process. The MWCNT/TPU fiber showed the highest tensile strength and ultra-high sensitivity with a gauge factor (GF) of approximately 2800 in the strain range of 5-100%. Due to its high strain sensitivity of conductivity, this CNT-reinforced composite fiber was able to be used to monitor the weight and shape of an object based on the 2D mapping of resistance changes. Moreover, the composite fiber was able to be stitched onto a highly stretchable elastic bandage using a sewing machine to produce a wearable strain sensor for the detection of diverse human motions. We also demonstrated the detection of finger motion by fabricating a smart glove at the joints. Due to its scalable production process, high stretchability and ultrasensitivity, the MWCNT/TPU fiber may open a new avenue for the fabrication of next-generation stretchable textile-based strain sensors.

Polyaniline-stabilized electromagnetic wave absorption composites of reduced graphene oxide on magnetic carbon nanotube film.

A multi-layered composite with exceptionally high electromagnetic wave-absorbing capacity and performance stability was fabricated via the facile electrophoresis of a reduced graphene oxide network on carbon nanotube (CNT)-Fe3O4-polyaniline (PANI) film. Minimum reflection loss (RL) of -53.2 dB and absorbing bandwidth of 5.87 GHz (< -10 dB) are achieved, surpassing most recently reported CNT- and graphene-based absorbers. In particular, comparing to the original composites, the minimum RL and bandwidth (< -10 dB) maintains 82.5% and 99.7%, respectively, after 20 h charge/discharge cycling, demonstrating high environmental suitability.

Superb electromagnetic wave-absorbing composites based on large-scale graphene and carbon nanotube films.

ABSTARCT: Graphene has sparked extensive research interest for its excellent physical properties and its unique potential for application in absorption of electromagnetic waves. However, the processing of stable large-scale graphene and magnetic particles on a micrometer-thick conductive support is a formidable challenge for achieving high reflection loss and impedance matching between the absorber and free space. Herein, a novel and simple approach for the processing of a CNT film-Fe3O4-large scale graphene composite is studied. The Fe3O4 particles with size in the range of 20-200 nm are uniformly aligned along the axial direction of the CNTs. The composite exhibits exceptionally high wave absorption capacity even at a very low thickness. Minimum reflection loss of -44.7 dB and absorbing bandwidth of 4.7 GHz at -10 dB are achieved in composites with one-layer graphene in six-layer CNT film-Fe3O4 prepared from 0.04 M FeCl3. Microstructural and theoretical studies of the wave-absorbing mechanism reveal a unique Debye dipolar relaxation with an Eddy current effect in the absorbing bandwidth.

Highly Sensitive Wearable Textile-Based Humidity Sensor Made of High-Strength, Single-Walled Carbon Nanotube/Poly(vinyl alcohol) Filaments.

Textile-based humidity sensors can be an important component of smart wearable electronic-textiles and have potential applications in the management of wounds, bed-wetting, and skin pathologies or for microclimate control in clothing. Here, we report a wearable textile-based humidity sensor for the first time using high strength (∼750 MPa) and ultratough (energy-to-break, 4300 J g-1) SWCNT/PVA filaments via a wet-spinning process. The conductive SWCNT networks in the filaments can be modulated by adjusting the intertube distance by swelling the PVA molecular chains via the absorption of water molecules. The diameter of a SWCNT/PVA filament under wet conditions can be as much as 2 times that under dry conditions. The electrical resistance of a fiber sensor stitched onto a hydrophobic textile increases significantly (by more than 220 times) after water sprayed. Textile-based humidity sensors using a 1:5 weight ratio of SWCNT/PVA filaments showed high sensitivity in high relative humidity. The electrical resistance increases by more than 24 times in a short response time of 40 s. We also demonstrated that our sensor can be used to monitor water leakage on a high hydrophobic textile (contact angle of 115.5°). These smart textiles will pave a new way for the design of novel wearable sensors for monitoring blood leakage, sweat, and underwear wetting.

Omnidirectionally Stretchable High-Performance Supercapacitor Based on Isotropic Buckled Carbon Nanotube Films.

The emergence of stretchable electronic devices has attracted intensive attention. However, most of the existing stretchable electronic devices can generally be stretched only in one specific direction and show limited specific capacitance and energy density. Here, we report a stretchable isotropic buckled carbon nanotube (CNT) film, which is used as electrodes for supercapacitors with low sheet resistance, high omnidirectional stretchability, and electro-mechanical stability under repeated stretching. After acid treatment of the CNT film followed by electrochemical deposition of polyaniline (PANI), the resulting isotropic buckled acid treated CNT@PANI electrode exhibits high specific capacitance of 1147.12 mF cm(-2) at 10 mV s(-1). The supercapacitor possesses high energy density from 31.56 to 50.98 µWh cm(-2) and corresponding power density changing from 2.294 to 28.404 mW cm(-2) at the scan rate from 10 to 200 mV s(-1). Also, the supercapacitor can sustain an omnidirectional strain of 200%, which is twice the maximum strain of biaxially stretchable supercapacitors based on CNT assemblies reported in the literature. Moreover, the capacitive performance is even enhanced to 1160.43-1230.61 mF cm(-2) during uniaxial, biaxial, and omnidirectional elongations.

High-Strength Single-Walled Carbon Nanotube/Permalloy Nanoparticle/Poly(vinyl alcohol) Multifunctional Nanocomposite Fiber.

Magnetic nanocomposite fibers are a topic of intense research due to their potential breakthrough applications such as smart magnetic-field-response devices and electromagnetic interference (EMI) shielding. However, clustering of nanoparticles in a polymer matrix is a recognized challenge for obtaining a property-controllable nanocomposite fiber. Another challenge is that the strength and ductility of the nanocomposite fiber decrease significantly with increased weight loading of magnetic nanoparticles in the fiber. Here, we report high-strength single-walled carbon nanotube (SWNT)/permalloy nanoparticle (PNP)/poly(vinyl alcohol) multifunctional nanocomposite fibers fabricated by wet spinning. The weight loadings of SWNTs and PNPs in the fiber were as high as 12.0 and 38.0%, respectively. The tensile strength of the fiber was as high as 700 MPa, and electrical conductivity reached 96.7 S m(-1). The saturation magnetization (Ms) was as high as 24.8 emu g(-1). The EMI attenuation of a fabric woven from the prepared fiber approached 100% when tested with electromagnetic waves with a frequency higher than 6 GHz. The present study demonstrates that a magnetic-field-response device can be designed using the fabricated multifunctional nanocomposite fiber.

Graphene-Based Fibers: A Review.

Motivated by their unique structure and excellent properties, significant progress has been made in recent years in the development of graphene-based fibers (GBFs). Potential applications of GBFs can be found, for instance, in conducting wires, energy storage and conversion devices, actuators, field emitters, solid-phase microextraction, springs, and catalysis. In contrast to graphene-based aerogels (GBAs) and membranes (GBMs), GBFs demonstrate remarkable mechanical and electrical properties and can be bent, knotted, or woven into flexible electronic textiles. In this review, the state-of-the-art of GBFs is summarized, focusing on their synthesis, performance, and applications. Future directions of GBF research are also proposed.

Stretchable Wire-Shaped Asymmetric Supercapacitors Based on Pristine and MnO2 Coated Carbon Nanotube Fibers.

While the emerging wire-shaped supercapacitors (WSS) have been demonstrated as promising energy storage devices to be implemented in smart textiles, challenges in achieving the combination of both high mechanical stretchability and excellent electrochemical performance still exist. Here, an asymmetric configuration is applied to the WSS, extending the potential window from 0.8 to 1.5 V, achieving tripled energy density and doubled power density compared to its asymmetric counterpart while accomplishing stretchability of up to 100% through the prestrainning-then-buckling approach. The stretchable asymmetric WSS constituted of MnO2/CNT hybrid fiber positive electrode, aerogel CNT fiber negative electrode and KOH-PVA electrolyte possesses a high specific capacitance of around 157.53 µF cm(-1) at 50 mV s(-1) and a high energy density varying from 17.26 to 46.59 nWh cm(-1) with the corresponding power density changing from 7.63 to 61.55 µW cm(-1). Remarkably, a cyclic tensile strain of up to 100% exerts negligible effects on the electrochemical performance of the stretchable asymmetric WSS. Moreover, after 10,000 galvanostatic charge-discharge cycles, the specific capacitance retains over 99%, demonstrating a long cyclic stability.

Laminated ultrathin chemical vapor deposition graphene films based stretchable and transparent high-rate supercapacitor.

Due to their exceptional flexibility and transparency, CVD graphene films have been regarded as an ideal replacement of indium tin oxide for transparent electrodes, especially in applications where electronic devices may be subjected to large tensile strain. However, the search for a desirable combination of stretchability and electrochemical performance of such devices remains a huge challenge. Here, we demonstrate the implementation of a laminated ultrathin CVD graphene film as a stretchable and transparent electrode for supercapacitors. Transferred and buckled on PDMS substrates by a prestraininig-then-buckling strategy, the four-layer graphene film maintained its outstanding quality, as evidenced by Raman spectra. Optical transmittance of up to 72.9% at a wavelength of 550 nm and stretchability of 40% were achieved. As the tensile strain increased up to 40%, the specific capacitance showed no degradation and even increased slightly. Furthermore, the supercapacitor demonstrated excellent frequency capability with small time constants under stretching.

Microstructural evolution of carbon nanotube fibers: deformation and strength mechanism.

A comprehensive investigation of the mechanical behavior and microstructural evolution of carbon nanotube (CNT) continuous fibers under twisting and tension is conducted using coarse-grained molecular dynamics simulations. The tensile strength of CNT fibers with random CNT stacking is found to be higher than that of fibers with regular CNT stacking. The factor dominating the mechanical response of CNT fibers is identified as individual CNT stretching. A simplified twisted CNT fiber model is studied to illustrate the structural evolution mechanisms of CNT fibers under tension. Moreover, it is demonstrated that CNT fibers can be reinforced by enhancing intertube interactions. This study would be helpful not only in the general understanding of the nano- and micro-scale factors affecting CNT fibers' mechanical behavior, but also in the optimal design of CNT fibers' architecture and performance.

Characterization of carbon nanotube fiber compressive properties using tensile recoil measurement.

The tensile properties of carbon nanotube (CNT) fibers have been widely studied. However, the knowledge of their compressive properties is still lacking. In this work, the compressive properties of both pure CNT fibers and epoxy infiltrated CNT fibers were studied using the tensile recoil measurement. The compressive strengths were obtained as 416 and 573 MPa for pure CNT fibers and CNT-epoxy composite fibers, respectively. In addition, microscopic analysis of the fiber surface morphologies revealed that the principal recoil compressive failure mode of pure CNT fiber was kinking, while the CNT-epoxy composite fibers exhibited a failure mode in bending with combined tensile and compressive failure morphologies. The effect of resin infiltration on CNT fiber compressive properties, including the compressive strength and the deformation mode, is discussed. This work expands the knowledge base of the overall mechanical properties of CNT fibers, which are essential for their application in multifunctional composites.

State of the art of carbon nanotube fibers: opportunities and challenges.

The superb mechanical and physical properties of individual carbon nanotubes (CNTs) have provided the impetus for researchers in developing high-performance continuous fibers based upon CNTs. The reported high specific strength, specific stiffness and electrical conductivity of CNT fibers demonstrate the potential of their wide application in many fields. In this review paper, we assess the state of the art advances in CNT-based continuous fibers in terms of their fabrication methods, characterization and modeling of mechanical and physical properties, and applications. The opportunities and challenges in CNT fiber research are also discussed.

Electrical conductivities of composites with aligned carbon nanotubes.

This paper reports an analysis of the effect of nanotube alignment on the electrical conductivity of carbon nanotube-based composites using a percolation model. Both straight and wavy nanotubes are considered. The thickness of an insulating matrix film between crossing nanotubes is randomly selected in the range of 0-1.8 nm and the resulting contact resistance is correspondingly determined based on the Simmon's formula. Results of Monte Carlo simulations indicate that the electrical conductivity of composites with aligned nanotubes is either lower or higher than that of composites with random nanotube orientation, depending on the degree of alignment and for wavy nanotubes the highest conductivity occurs when nanotube are slightly aligned. The anisotropy of conductivity is also found strongly affected by nanotube alignment especially when the nanotube contents are small. The findings reached in this study coincide with some experimental observations on carbon nanotube-based composites.

Real-time in situ sensing of damage evolution in advanced fiber composites using carbon nanotube networks.

Developments in producing nanostructured materials with novel properties have opened up new opportunities in which unique functionality can be added to existing material systems. As advanced fiber composites are utilized more frequently in primary structural applications there is a key challenge to enhance the performance and reliability while reducing maintenance. As a consequence there is tremendous scientific and technical interest in the development of techniques for monitoring the health of composite structures where real-time sensing can provide information on the state of microstructural damage. In this research we utilize electrically conductive networks of carbon nanotubes as in situ sensors for detecting damage accumulation during cyclic loading of advanced fiber composites. Here we show that, by combining load and strain measurements in real-time with direct current electrical resistance measurements of the carbon nanotube network, insight can be gained toward the evolution and accumulation of damage. The resistance/strain relations show substantial hysteresis due to the formation and opening/closing of cracks during cyclic loading. Through interpreting the resistance response curves we identify a parameter that may be utilized as a quantitative measure of damage.

Static and dynamic properties of single-walled boron nitride nanotubes.

This paper reports the study of the static and dynamic properties of single-walled boron nitride nanotubes by using the molecular structural mechanics approach. The stiffness parameters of the boron-nitride bond are based on the DREIDING force field. The effects of tube diameter and chirality are investigated. The computational results show that the Young's modulus and the shear modulus of boron nitride nanotubes increase monotonically with nanotube diameter and reach up to 0.9 TPa and 0.5 TPa, respectively, at large tube diameter. The nanotube chirality has only slight effects on the moduli only when tube diameters are small. The fundamental frequencies of boron nitride nanotubes are found to be dependent not only on the nanotube aspect ratio but also on the tube diameter.

Charge-induced strains in single-walled carbon nanotubes.

This paper investigates the electromechanical coupling in single-walled carbon nanotubes. In the model system, the extra electric charge of the nanotube is assumed to be uniformly distributed on carbon atoms. The electrostatic interactions between charged carbon atoms are calculated using the Coulomb law. The deformation of the charged nanotube is obtained by using the molecular structural mechanics method and considering the electrostatic interactions as an external loading acting on carbon atoms. The axial strain is found to be a symmetric function of applied charge, and our predictions are in very good agreement with those from ab initio calculations. The present results indicate that the nanotube aspect ratio has a strong effect on the axial strain when the ratio is less than 10 and the general trend is that the strain increases with the aspect ratio. The peak axial and radial strains occur at nanotube diameters of around 1.2-1.5 nm.